CN109678511A - 一种致密HfC(Si)-HfB2复相陶瓷的制备方法 - Google Patents

一种致密HfC(Si)-HfB2复相陶瓷的制备方法 Download PDF

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CN109678511A
CN109678511A CN201811576879.9A CN201811576879A CN109678511A CN 109678511 A CN109678511 A CN 109678511A CN 201811576879 A CN201811576879 A CN 201811576879A CN 109678511 A CN109678511 A CN 109678511A
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hfc
hfb
complex phase
preparation
densification
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CN109678511B (zh
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郝巍
赵晓峰
倪娜
蔡黄越
姚尧
易妹玉
郭芳威
肖平
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Shanghai Jiaotong University
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Priority to PCT/CN2019/090157 priority patent/WO2020133928A1/zh
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Abstract

本发明涉及一种致密HfC(Si)‑HfB2复相陶瓷的制备方法，将氧化铪粉体、纳米碳黑以及六硼化硅粉体按摩尔比为1～10∶1～20∶1～5的比例混合，获得混合粉体，经过进行球磨混合均匀，然后进行干燥，形成均匀的混合粉体；将得到的均匀混合粉体装入石墨模具中进行放电等离子体烧结，即原位碳‑硼热还原反应‑烧结致密化一步工艺完成，制备得到致密度为94.0％～100％且晶粒均匀弥散分布的HfC(Si)‑HfB2复相陶瓷。与现有技术相比，本发明烧结制备得到物相组成和晶粒尺寸均匀分布，同时其陶瓷烧结体具有较高的致密性和断裂韧性，避免传统先制备粉体过程中难以控制成分和晶粒尺寸，后期烧结陶瓷过程中难以致密化。

Description

一种致密HfC(Si)-HfB2复相陶瓷的制备方法
技术领域
本发明涉及超高温陶瓷的制备方法，尤其是涉及一种致密HfC(Si)-HfB2复相陶瓷的制备方法。
背景技术
超高温陶瓷(Ultra-high temperature ceramics，UHTCs)材料是一种新型的高温耐烧蚀的结构材料，其具有很高的熔点(>2000℃)，高的硬度和杨氏模量，在高温条件下具有高的强度，低的热膨胀系数以及具有较好的热物理化学稳定性，高的热导率和电导率。最重要其具有较好的抗烧蚀性能而被应用于超音速飞机和固体火箭的热结构部件，例如喷管，机翼前缘以及发动机的热端部件；同时还应用于高温电极和切削刀具，因此备受广泛的关注。超高温陶瓷大多是元素周期表中第Ⅳ族和Ⅴ族过渡金属元素的碳化物(HfC，ZrC，TaC，NbC)，硼化物(HfB2，ZrB2，TaB2)以及氮化物(HfN，ZrN)，以及一些难熔金属合金和碳/碳复合材料(Ta，W，Ir和C/C复合材料)。目前，碳化物是熔点最高且更耐高温的超高温陶瓷材料，尤其是HfC材料其熔点最高可达到3980℃，热膨胀系数仅为6.73×10-6/℃，密度与其他碳化物相比较为适中(ρ＝12.7g·cm-3)。但是HfC具有以下缺陷而阻止其被广泛应用于航空航天领域，主要有以下几点：一方面，陶瓷熔点较高，具有较低的自扩散系数，难以烧结致密化；其次，其作为高温结构材料而言，断裂韧性较低(2.1-3.4MPa·m1/2)；最后，其作为高温抗烧蚀材料，容易被氧化即当服役温度达到500℃以上有氧环境下材料开始氧化，这也限制了其在高温领域的应用。同时，HfB2陶瓷也具有高的熔点(3380℃)、高硬度(29GPa)和杨氏模量(480GPa)，高的电导率(9.1×106S·m-1)和热导率(74-114W·(m K)-1)，然而具有低的热膨胀系数为6.3×10-6/℃，较低的断裂韧性(3.0-6.0MPa·m1/2)。与HfC相比，单相HfB2在1200℃以下具有良好的抗氧化性能，这是由于液态B2O3玻璃相生成起到了良好的抗氧化作用。无论是HfC陶瓷还是HfB2陶瓷的难以烧结致密化和断裂韧性低成为当前研究应用的瓶颈。因此HfC和HfB2等UTHCs的烧结和韧性问题成为近年来国内外研究的热点之一。同时烧结制备固溶体复相超高温陶瓷对其烧结和力学方面的应用具有重要的意义。
因此，制备复相陶瓷被认为是提高超高温陶瓷烧结和断裂韧性的最有效的方法，并且同时可以引入原位反应烧结促使元素在高温中扩散迁移，进而达到快速烧结致密化。到目前为止，已报道的制备HfC和HfB2陶瓷制备方法有以下几种，例如以炭黑、石墨和HfO2为原料，采用碳热还原法先制备粉体后烧结制成HfC陶瓷[Ji-Xuan Liu,Yan-Mei Kan,Guo-Jun Zhang.Synthesis of Ultra-Fine Hafnium Carbide Powder and its PressurelessSintering[J].Journal of the American Ceramic Society,93(2010)980-986.]、以HfO2和WC为原料，采用反应烧结法制备HfC-W金属陶瓷和HfC-SiC陶瓷[Shi-Kuan Sun,Guo-JunZhang,Ji-Xuan Liu,et al.Reaction Sintering of HfC/W Cermets with HighStrength and Toughness[J].Journal of the American Ceramic Society,96(2013)867-872.]和[Lun Feng,Sea-Hoon Lee,Jie Yin.Low-Temperature Sintering of HfC/SiC Nanocomposites Using HfSi2-C Additives[J].Journal of the American CeramicSociety,99(2016)2632-2638.]。以及采用HfCl4和酚醛树脂分别作为Hf源和碳源，用溶胶-凝胶法制备纳米HfC粉体及涂层[S.Venugopal1,A.Paul1,B.Vaidhyanathan et al.,Nano-crystalline ultra high temperature HfB2and HfC powders and coatings using aSol-Gel approach[J].Advanced Ceramic Coatings and Materials for ExtremeEnvironments.32(2011)151-160.]。另外采用化学气相沉积法(CVD)制备HfC抗烧蚀涂层[Jincui Ren,Yulei Zhang,Jinhua Li,et al.,Effects of deposition temperatureand time on HfC nanowires synthesized by CVD on SiC-coated C/C composites[J].Ceramics International.42(2016)5623-5628.]和化学气相渗透法(CVI)，反应熔融浸渗法(RMI)以及前驱体浸渍裂解法(PIP)制备超高温陶瓷复合材料[Sufang Tang,ChenglongHu.Design,Preparation and Properties of Carbon Fiber Reinforced Ultra-HighTemperature Ceramic Composites for Aerospace Applications:A Review[J].Journalof Materials Science&Technology.33(2017)117-130.]。以上采用的方法制备HfC和HfB2陶瓷和涂层的方法，均需要在高于1500℃的条件下发生反应先制得粉体，然后在高于2000℃的高温条件下烧结。需要两步完成且高温下无法控制其物相组成和晶粒尺寸，同时难熔的HfO2原料难以在低温下(<1500℃)扩散反应。另外，CVD法仅限于沉积HfC涂层或者纳米线且制备效率低，工艺难以控制。CVI，RMI和PIP用于制备超高温陶瓷复合材料，很难获得较为致密的烧结体，并且还可能引入杂质，同时对设备要求较高，工艺时间长和成本高。同时所制备HfC的前驱体难以获得，成本较高。除此之外，近年来UHTCs的烧结方法有放电等离子体烧结(SPS)[Omar Cedillos-Barraza,Salvatore Grasso,Nasrin Al Nasiri,et al.,Sintering behavior,solid solution formation and characterization of TaC,HfCand TaC-HfC fabricated by spark plasma sintering[J].Journal of the EuropeanCeramic Society.36(2016)1539–1548.]，热压烧结(Hot pressing)[Liuyi Xiang,LaifeiCheng,Yi Hou,et al.,Fabrication and mechanical properties of laminated HfC-SiC/BN ceramics[J].Journal of the European Ceramic Society 34(2014)3635-3640]和[E.Zapata-Solvas,D.D.Jayaseelan,H.T.Lin,P.Brown,W.E.Lee.Mechanicalproperties of ZrB2-and HfB2-based ultra-high temperature ceramics fabricatedby spark plasma sintering[J].Journal of the European Ceramic Society 33(2013)1373–1386.]以及无压烧结[Ji-Xuan Liu,Yan-Mei Kan,Guo-Jun Zhang.Synthesis ofUltra-Fine Hafnium Carbide Powder and its Pressureless Sintering[J].Journalof the American Ceramic Society 93(2010)980–986.]。以上已报道的HfC和HfB2陶瓷的烧结方法仅仅是陶瓷烧结过程，并没有原位反应过程，并且均需要较高的烧结温度(1800-2400℃)，进而烧结工艺难以控制。因此，原位反应烧结可以有效解决HfC和HfB2超高温陶瓷烧结的问题，同时低温制备可以有效调控晶粒尺寸。并且到目前为止，引入耐高温的SiB6作为原位反应的硼源和硅源，以纳米碳黑为碳源，采用放电等离子体烧结法(SPS)，通过原位碳-硼热还原反应烧结法一步制备HfC(Si)-HfB2复相陶瓷方面的研究还很少见报道。
中国专利CN100378035C公开了一种硼化物—碳化硅复相陶瓷及其制备方法，其特征在于利用聚碳硅烷裂解时生成的碳化硅的活性，在1700～1900℃温和温度下热压制备致密的硼化物—碳化硅复合陶瓷；所述硼化物主要包括硼化锆，硼化钛和硼化铪；这种工艺不需添加其他助烧剂，保证了材料的高温性能；在制备过程中加入1-12wt％的硅，锆，钛，铪等金属粉末，或者这些金属粉末的任意组合，以吸收聚碳硅烷裂解过程中的残留碳，则可以提高复合材料的致密度，改善材料的力学性能。但是由于起始原料与本申请的区别，导致其无法在1500-1850℃的温度条件下发生碳-硼热还原反应烧结过程，并且由于制备工艺的差异，无法提升复相陶瓷韧性。
发明内容
本发明的目的在于克服上述超高温陶瓷粉末难以合成和块体陶瓷难以烧结的现有技术缺点，在引入耐高温氧化的SiB6作为硼源和硅源，纳米碳黑作为碳源，纳米氧化铪作为铪源，通过原位碳-硼热还原反应烧结一步完成制备HfC(Si)-HfB2复相陶瓷，并且在放电等离子体烧结过程中，SiB6和碳黑具有较好的高温电导率，有效提高反应体系放电烧结效率，并且B、C、Si元素、扩散迁移速率快，高效快速地实现原位碳化、硼化以及扩散固溶反应。烧结制备得到物相组成和晶粒尺寸均匀分布，同时其陶瓷烧结体具有较高的致密性和断裂韧性，避免传统先制备粉体过程中难以控制成分和晶粒尺寸，后期烧结陶瓷过程中难以致密化。因此，本发明提供了一种不仅工艺简单而且高效快速烧结制备HfC(Si)-HfB2复相陶瓷，实现了碳化铪和硼化铪陶瓷的原位复合进而优化提升其性能，具有广阔的应用前景。
本发明的目的可以通过以下技术方案来实现：
一种致密HfC(Si)-HfB2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为50-500nm氧化铪粉体(HfO2)、纳米碳黑(50nm)以及颗粒尺寸为1-5μm的六硼化硅粉体(SiB6)，按照摩尔比为：HfO2∶C∶SiB6＝(1～10)∶(1～20)∶(1～5)的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO2、炭黑以及SiB6均匀混合，混合粉体与球石的质量比为1∶(4～20)，球磨机转速为200-500转，球磨6-24h，然后在50-80℃电热鼓风干燥箱中干燥4-10h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1500-1850℃，保温时间为5-30min，烧结施加压力为20-60MPa，升温速率为50-200℃/min，真空度控制在0-1.0mbar，即可得到致密度为94.0％～100％且晶粒均匀弥散分布的HfC(Si)-HfB2复相陶瓷。
与目前现有公开的技术，例如CN100378035C相比，本申请存在以下区别技术特征：
(1)起始原料不同：本申请采用氧化铪粉体、纳米碳黑以及六硼化硅粉体作为原料，无论在化学热力学还是动力学方面，这些原料都可以在1500-1850℃的温度条件下发生碳-硼热还原反应烧结过程。同时通过大量实验验证，反应物体系简单且易发生反应烧结，制备出所需要的HfC(Si)-HfB2复相陶瓷，且生成产物的组成和纯度容易控制且无太多杂质产生；
(2)工艺制备方法不同：本申请采用放电等离子体烧结法，通过碳-硼热还原反应烧结过程制备致密的HfC(Si)-HfB2陶瓷，烧结加热机制不同导致最终反应物反应机理不同。另外本申请通过引入纳米碳黑为碳源，一方面作为碳源，促进碳-硼热还原反应；另一方面作为晶界相，调控反应体系的电导率进而放电等离子体烧结效率，有利于提高复相陶瓷韧性；
(3)最终生成物的组成和微观结构不同：本申请目标产物是HfC基复相陶瓷，通过引入SiB6和纳米碳黑经过碳-硼热还原反应烧结制备致密的HfC(Si)-HfB2复相陶瓷，生成物中有HfC和HfB2晶粒弥散分布且Si元素扩散进入HfC晶格形成固溶体，纳米碳黑均匀分布在晶界处，有效提高复相陶瓷的断裂韧性。
与现有技术相比，本发明具有以下优点：
(1)采用原位碳-硼热还原一步反应烧结法制备成分和晶粒尺寸可控的HfC(Si)-HfB2复相陶瓷。
(2)同时结合SPS低温高效快速反应烧结获得HfC(Si)-HfB2复相陶瓷致密且不同物相晶粒均匀分布、并且伴随元素扩散形成固溶体，这样大大提高了陶瓷烧结致密化过程。
(3)这种一步法反应烧结制备HfC(Si)-HfB2复相陶瓷工艺简单，两相成分可控，原料易得，效率高。
(4)这种方法制备的HfC(Si)-HfB2复相陶瓷的断裂韧性具有明显的提高，采用三点弯曲单边开口梁的方法测试其断裂韧性可以达到8.52-14.3MPa·m1/2，同时能在2500℃的乙氧炔火焰烧蚀180s，其线烧蚀率均小于6μm·s-1。
(5)本申请所涉及的技术参数，例如起始反应粉体颗粒尺寸、配比、球磨工艺参数以及放电等离子体烧结时采用的温度、压力、真空度等都是通过大量实验和基于化学热力学以及动力学反应机制后总结的结果。只有在上述技术参数：配比、烧结温度、压力和保温时间的条件下才能发生原位碳-硼热还原一步反应烧结，制备出致密的HfC(Si)-HfB2复相陶瓷。反之，颗粒尺寸和配比不是上述参数，温度太高，压力过大，会导致晶粒异常长大，导致陶瓷结构和性能变差；温度太低、压力太小，会导致原位碳-硼热还原一步反应烧结致密化过程无法实现，没有达到起始原料反应的活化能，另外压力过小材料无法烧结致密化。最后影响材料的结构，进而使得材料的力学性能和高温抗烧蚀性能变差。真空度过高，氧分压过高会导致反应物氧化，原位碳-硼热还原反应无法进行；真空度过低，对设备要求过高，也无法正常获得目标材料。
附图说明
图1为实施例3制备的HfC(Si)-HfB2复相陶瓷的XRD图谱；
图2为实施例3制备的HfC(Si)-HfB2复相陶瓷的SEM图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
一种致密HfC(Si)-HfB2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为50-500nm氧化铪粉体(HfO2)、纳米碳黑(50nm)以及颗粒尺寸为1-5μm的六硼化硅粉体(SiB6)，按照摩尔比为：HfO2∶C∶SiB6＝(1～10)∶(1～20)∶(1～5)的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO2、炭黑以及SiB6均匀混合，混合粉体与球石的质量比为1∶(4～20)，球磨机转速为200-500转，球磨6-24h，然后在50-80℃电热鼓风干燥箱中干燥4-10h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1500-1850℃，保温时间为5-30min，烧结施加压力为20-60MPa，升温速率为50-200℃/min，真空度控制在0-1.0mbar，即可得到致密度为94.0％～100％且晶粒均匀弥散分布的HfC(Si)-HfB2复相陶瓷。
以上方法中使用的HfO2纳米粉体是由上海超微纳米科技有限公司生产的，纯度≥99.9％。异丙醇的纯度≥99.8％。纳米碳黑是由北京伊诺凯科技有限公司生产的，纯度≥99.9％。六硼化硅粉体是由阿法埃莎公司生产的，纯度≥98％。
球磨工艺采用的是行星球磨机，是由南京大学生产的型号为QM-3SP4型行星球磨机。干燥采用的是电热鼓风干燥箱，是由上海一恒科学仪器有限公司生产的DHG-9075A型。放电等离子体烧结炉(SPS)为德国FCT公司生产的HPD-25放电等离子体烧结系统。
以下是更加详细的实施案例，通过以下实施案例进一步说明本发明的技术方案以及所能够获得的技术效果。
实施例1：
一种致密HfC(Si)-HfB2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为50nm氧化铪粉体(HfO2)、纳米碳黑(50nm)以及颗粒尺寸为5μm的六硼化硅粉体(SiB6)，按照摩尔比为：HfO2∶C∶SiB6＝5∶2∶1的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO2、炭黑以及SiB6均匀混合，混合粉体与球石的质量比为1∶10，球磨机转速为300转，球磨8h，然后在50℃电热鼓风干燥箱中干燥6h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1600℃，保温时间为10min，烧结施加压力为45MPa，升温速率为200℃/min，真空度控制在0mbar，即可得到致密度为96％且晶粒均匀弥散分布的HfC(Si)-HfB2复相陶瓷。
实施例2：
一种致密HfC(Si)-HfB2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为100nm氧化铪粉体(HfO2)、纳米碳黑(50nm)以及颗粒尺寸为4μm的六硼化硅粉体(SiB6)，按照摩尔比为：HfO2∶C∶SiB6＝10∶5∶3的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO2、炭黑以及SiB6均匀混合，混合粉体与球石的质量比为1∶15，球磨机转速为350转，球磨12h，然后在60℃电热鼓风干燥箱中干燥8h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1700℃，保温时间为20min，烧结施加压力为35MPa，升温速率为100℃/min，真空度控制在0.5mbar，即可得到致密度为98％且晶粒均匀弥散分布的HfC(Si)-HfB2复相陶瓷。
实施例3：
一种致密HfC(Si)-HfB2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为200nm氧化铪粉体(HfO2)、纳米碳黑(50nm)以及颗粒尺寸为1μm的六硼化硅粉体(SiB6)，按照摩尔比为：HfO2∶C∶SiB6＝2∶1∶1的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO2、炭黑以及SiB6均匀混合，混合粉体与球石的质量比为1∶20，球磨机转速为400转，球磨16h，然后在70℃电热鼓风干燥箱中干燥10h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1850℃，保温时间为30min，烧结施加压力为60MPa，升温速率为80℃/min，真空度控制在0.2mbar，即可得到致密度为99％且晶粒均匀弥散分布的HfC(Si)-HfB2复相陶瓷。
实施例4：
一种致密HfC(Si)-HfB2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为80nm氧化铪粉体(HfO2)、纳米碳黑(50nm)以及颗粒尺寸为1μm的六硼化硅粉体(SiB6)，按照摩尔比为：HfO2∶C∶SiB6＝1∶1∶1的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO2、炭黑以及SiB6均匀混合，混合粉体与球石的质量比为1∶4，球磨机转速为200转，球磨24h，然后在50℃电热鼓风干燥箱中干燥10h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1500℃，保温时间为30min，烧结施加压力为20MPa，升温速率为50℃/min，真空度控制在0mbar，即可得到致密度为94.0％且晶粒均匀弥散分布的HfC(Si)-HfB2复相陶瓷。
实施例5：
一种致密HfC(Si)-HfB2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为200nm氧化铪粉体(HfO2)、纳米碳黑(50nm)以及颗粒尺寸为4μm的六硼化硅粉体(SiB6)，按照摩尔比为：HfO2∶C∶SiB6＝10∶15∶3的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO2、炭黑以及SiB6均匀混合，混合粉体与球石的质量比为1∶12，球磨机转速为200-500转，球磨12h，然后在60℃电热鼓风干燥箱中干燥6h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1650℃，保温时间为20min，烧结施加压力为40MPa，升温速率为100℃/min，真空度控制在0.5mbar，即可得到致密度为98％且晶粒均匀弥散分布的HfC(Si)-HfB2复相陶瓷。
实施例6：
一种致密HfC(Si)-HfB2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为500nm氧化铪粉体(HfO2)、纳米碳黑(50nm)以及颗粒尺寸为5μm的六硼化硅粉体(SiB6)，按照摩尔比为：HfO2∶C∶SiB6＝8∶20∶5的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO2、炭黑以及SiB6均匀混合，混合粉体与球石的质量比为1∶20，球磨机转速为500转，球磨6h，然后在80℃电热鼓风干燥箱中干燥4h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1850℃，保温时间为5min，烧结施加压力为60MPa，升温速率为200℃/min，真空度控制在1.0mbar，即可得到致密度为100％且晶粒均匀弥散分布的HfC(Si)-HfB2复相陶瓷。
图1为实施例3制备的HfC(Si)-HfB2复相陶瓷的XRD图谱，由图1可看出本发明所制备的HfC(Si)-HfB2复相陶瓷的XRD图谱：主晶相为HfC和HfB2，并且结晶性较好，其中存在少量HfO2。HfC和HfB2晶相分别与PDF NO.65-8747和PDF NO.65-8678相吻合。图2为实施例3所制备HfC(Si)-HfB2复相陶瓷的SEM图。由图2可看出本发明实施例3所制备的HfC(Si)-HfB2复相陶瓷中，HfC和HfB2晶粒均匀弥散分布且陶瓷致密较高，晶粒尺寸约为600nm，晶界处存在少量游离的碳。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (10)

1.一种致密HfC(Si)-HfB2复相陶瓷的制备方法，其特征在于，该方法采用以下步骤：
(1)将氧化铪粉体、纳米碳黑以及六硼化硅粉体按摩尔比为1～10∶1～20∶1～5的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，使氧化铪粉体、纳米碳黑以及六硼化硅粉体均匀混合，然后进行干燥，形成均匀的混合粉体；
(3)将得到的均匀混合粉体装入石墨模具中进行放电等离子体烧结，制备得到致密度为94.0％～100％且晶粒均匀弥散分布的HfC(Si)-HfB2复相陶瓷。
2.根据权利要求1所述的一种致密HfC(Si)-HfB2复相陶瓷的制备方法，其特征在于，步骤(1)中所述氧化铪粉体的粒径为50-500nm，所述纳米碳黑的粒径为50nm，所述六硼化硅粉体的粒径为1-5μm。
3.根据权利要求1所述的一种致密HfC(Si)-HfB2复相陶瓷的制备方法，其特征在于，步骤(2)中采用行星式球磨机对混合粉体进行球磨。
4.根据权利要求1所述的一种致密HfC(Si)-HfB2复相陶瓷的制备方法，其特征在于，步骤(2)中球磨时采用的介质为异丙醇。
5.根据权利要求1所述的一种致密HfC(Si)-HfB2复相陶瓷的制备方法，其特征在于，步骤(2)中球磨时混合粉体与采用球石的质量比为1∶4～20。
6.根据权利要求3所述的一种致密HfC(Si)-HfB2复相陶瓷的制备方法，其特征在于，步骤(2)中球磨时控制球磨机转速为200-500转，球磨6-24h。
7.根据权利要求1所述的一种HfC(Si)-HfB2致密复相陶瓷的制备方法，其特征在于，步骤(2)中球磨结束后在50-80℃电热鼓风干燥箱中干燥4-10h。
8.根据权利要求1所述的一种致密HfC(Si)-HfB2复相陶瓷的制备方法，其特征在于，步骤(3)中所述模具为铺有石墨纸的石墨模具。
9.根据权利要求1所述的一种致密HfC(Si)-HfB2复相陶瓷的制备方法，其特征在于，步骤(3)进行放电等离子体烧结时控制烧结温度为1500-1850℃，保温时间为5-30min，烧结施加压力为20-60MPa，升温速率为50-200℃/min，真空度控制在0-1.0mbar。
10.根据权利要求1所述的一种致密HfC(Si)-HfB2复相陶瓷的制备方法，其特征在于，步骤(3)进行放电等离子体烧结时控制烧结温度优选为1500-1650℃。
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CN110372386A (zh) * 2019-08-14 2019-10-25 山东理工大学 一种低温液相热压烧结制备致密碳化钽陶瓷的方法
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