CN114853477A - 一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷及其制备方法 - Google Patents

一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷及其制备方法 Download PDF

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CN114853477A
CN114853477A CN202210471446.7A CN202210471446A CN114853477A CN 114853477 A CN114853477 A CN 114853477A CN 202210471446 A CN202210471446 A CN 202210471446A CN 114853477 A CN114853477 A CN 114853477A
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entropy
ablation
carbide
silicon carbide
boride
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CN114853477B (zh
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郝巍
陈鑫悦
周春妮
秦潇娴
王冬云
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Zhejiang Normal University CJNU
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Abstract

本发明涉及一种耐烧蚀高熵碳化物‑高熵硼化物‑碳化硅复相陶瓷及其制备方法，该方法包括以下步骤：(1)将过渡金属氧化物混合粉体、纳米碳黑和SiB6粉体混合，形成前躯体粉体；(2)将前躯体粉体进行无压反应烧结，得到致密度可达96％以上的耐烧蚀高熵碳化物‑高熵硼化物‑碳化硅复相陶瓷。与现有技术相比，本发明以SiB6为Si源和B源，通过碳‑硼‑硅化反应和固溶协同增效无压反应烧结法制备兼具优异高温抗氧化和耐烧蚀性能，且Si和B协同诱导陶瓷烧蚀后形成致密且稳定的氧化保护层的高熵超高温复相陶瓷。不仅制备方法简单、成本低，而且元素组成和结构、块体尺寸可控，具有广阔的发展前景。

Description

一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷及其制 备方法
技术领域
本发明涉及热防护材料领域，具体涉及一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷及其制备方法。
背景技术
高超声速飞行器的热防护系统和热结构关键部件亟需极端环境下耐高温(>2000℃)、抗氧化且耐烧蚀(抗氧化和抵抗机械冲刷、剪切等)的超高温结构材料。高熵碳化物陶瓷是一种由等摩尔或接近等摩尔比的5种或5种以上的过渡金属元素和碳元素形成的具有NaCl结构的单相化合物。“熵稳定”的单相结构使其具有：①热力学上的高熵效应；②结构上的晶格畸变效应；③动力学上的迟滞扩散效应；④性能上的鸡尾酒效应。与单组元或二元碳化物陶瓷相比，高熵碳化物陶瓷不仅具有优异的高温稳定性、高温强度、抗蠕变性能及较高的弹性模量、硬度等，而且表现出较好的抗氧化性能，被认为是目前高超声速飞行器的热防护系统、鼻锥及机翼导向前缘等热结构关键部件最有潜力的材料。
通过对比高熵碳化物形成的理论计算和实验研究结果得出，(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C陶瓷体系是目前高温稳定性和综合性能最优的高熵碳化物陶瓷，备受重点关注。但是，一方面，(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C陶瓷由于其中5种过渡金属元素氧化速率不同，即各过渡金属原子与氧的结合能力排序为Hf>Zr>Ti>Ta>Nb，导致高温氧化后生成多层结构氧化物，且氧化层中残余应力和高温蠕变会导致氧化层剥离和脱落，这将大大降低其抗氧化性能；另一方面，(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C陶瓷烧蚀后表面氧化层呈现多孔疏松结构，易被机械剥离，造成基体进一步烧蚀失效。因此，高熵碳化物陶瓷的高温抗氧化和耐烧蚀问题已经成为国内外研究者重点关注的问题，同时对其在严苛极端环境下的应用具有重要的意义。
为了提高上述高熵碳化物陶瓷的抗氧化和耐烧蚀性能，近年来研究者们主要提出以下两种方法：
(1)元素掺杂改性法[Z.Peng,W.Sun,X.Xiong,et al.Novel refractory high-entropy ceramics:Transition metal carbonitrides with superior ablationresistance[J].Corrosion Science,2021,184:109359.]，此方法将(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C陶瓷中C元素用N元素部分取代，非金属元素位置的掺杂取代再次引起高熵体系的晶格畸变，造成烧蚀后氧化层中氧化物呈梯度分布，烧蚀中心区为多孔结构的Hf、Zr复合氧化物，而烧蚀边缘区为熔融态Ta、Nb复合氧化物。随着烧蚀温度升高和烧蚀时间延长，多孔结构为O2扩散提供通道，Ta、Nb的氧化物粘度大、流动性差无法愈合氧化层中的孔洞，造成基体进一步氧化，导致陶瓷烧蚀失效。
(2)制备高熵碳化物复相陶瓷。北京理工大学王一光教授等制备了(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C陶瓷[H.X.Wang,X.Han,W.Liu,et al.Oxidation behavior ofhigh-entropy carbide(Hf0.2Ta0.2Zr0.2Ti0.2Nb0.2)C at 1400-1600℃[J].CeramicsInternational,2021,47(8):10848-10854.]和(Hf0.2Zr0.2Ta0.2Ti0.2Nb0.2)C-SiC复相陶瓷[H.X.Wang,Y.J.Cao,W.Liu,et al.Oxidation behavior of(Hf0.2Ta0.2Zr0.2Ti0.2Nb0.2)C-xSiC ceramics at high temperature[J].Ceramics International,2020,46(8):11160-11168.]。对比研究发现：单相(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C陶瓷氧化过程中，气态TiO向外扩散、挥发导致氧化层中形成大量孔洞，同时由于过渡金属选择性氧化，Hf、Zr、Ti协同抑制Ta和Nb的扩散，高温下Hf、Zr、Ti氧化较为明显，而Ta和Nb氧化较为缓慢，这样导致形成多孔疏松且多层结构的氧化物，对抗氧化性能不利。向其中引入SiC，制备(Hf0.2Zr0.2Ta0.2Ti0.2Nb0.2)C-SiC高熵复相陶瓷，消除了气态TiO挥发造成的孔洞，诱导形成致密硅酸盐氧化保护层，有效提升高熵碳化物的抗氧化性能。但是，引入过量的Si争夺O2，进一步与Hf、Zr、Ti协同抑制Ta和Nb的扩散，长时间氧化后形成疏松且多层结构的氧化物，又会降低其抗氧化性能。为了解决以上问题，必须兼顾高熵超高温复相陶瓷氧化、烧蚀后致密氧化层的形成与气体挥发产生孔洞的自愈合。
可见，将B引入高熵碳化物和SiC复相陶瓷中，一方面，高温烧蚀氧化生成的B2O3可以有效调控硅酸盐氧化层的粘度和流动性，既能满足富含Si和B的致密氧化层形成，又能及时自愈合孔洞等缺陷，实现高效氧化防护的目标；另一方面，低熔点的B2O3和挥发性气体产物逸出会降低陶瓷表面热量，又能够释放氧化层中热应力，达到超高温自发汗冷却的目的。基于此，提出一种将Si和B同时引入高熵碳化物中，制备高熵碳化物-高熵硼化物-碳化硅复相陶瓷的新方法。
到目前为止，高熵超高温复相陶瓷的制备方法主要有以下几种：热压烧结法(Hotpressing)、放电等离子烧结法(Spark plasma sintering，SPS)、电弧熔化法(Arcmelting)、无压烧结法(Pressureless sintering)等。华南理工大学褚衍辉教授采用热压法制备了(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C陶瓷[B.L.Ye,T.Q.Wen,Y.H.Chu.High-temperatureoxidation behavior of(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)Chigh-entropy ceramics in air[J].Journal of the American Ceramic Society,2020,103(1):500-507.]。同时，东华大学刘吉轩研究员采用热压法制备了(Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2-SiC复相陶瓷[J.X.Liu,X.Q.Shen,Y.Wu,et al.Mechanical properties of hot-pressed high-entropydiboride-based ceramics[J].Journal of Advanced Ceramics,2020,9(4):503-510.]。上述采用热压法仅仅适合制备小尺寸样品，不能制备大尺寸且形状复杂的陶瓷。此外，研究者们以(Hf0.2Zr0.2Ta0.2Ti0.2Nb0.2)C和SiC粉体为原料，采用SPS制备(Hf0.2Zr0.2Ta0.2Ti0.2Nb0.2)C-SiC高熵复相陶瓷[K.Lu,J.X.Liu,X.F.Wei,etal.Microstructures and mechanical properties of high-entropy(Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C ceramics with the addition of SiC secondary phase[J].Journal of the European Ceramic Society,2020,40(5):1839-1847.]。
SPS虽然可以快速实现高熵复相陶瓷烧结致密化，但是外加SiC的方式容易导致其在复相陶瓷中分布不均匀。同时，美国加州大学圣地亚哥分校骆建教授团队以对应过渡金属碳化物和硼化物为原料，采用反应SPS制备了(TiZrNbHfTaW)C-(TiZrNbHfTaW)B2复相陶瓷[M.D.Qin,J.Gild,C.Z.Hu,et al.Dual-phase high-entropy ultra-high temperatureceramics[J].Journal of the European Ceramic Society,2020,40(15):5037-5050.]。但是，SPS制备高熵超高温陶瓷有以下两点缺陷：一方面，碳化物之间和硼化物之间反应活化能较低，反应烧结致密化较为困难，需要在2200℃高温下才能反应固溶完成，这样造成晶粒异常长大，晶界处存在气孔；另一方面，SPS仅限于小尺寸样品的制备，不能进行复杂形状、大尺寸样品的制备。再者，电弧熔化法制备高熵碳化物陶瓷[M.Biesuz,T.G.Saunders,J.Veverka,et al.Solidification microstructures of multielement carbides inthe high entropy Zr-Nb-Hf-Ta-Cx system produced by arcmelting[J].ScriptaMaterialia,2021,203:114091和A.Y.Pak,P.S.Grinchuk,A.A.Gumovskaya,etal.Synthesis of transition metal carbides and high-entropy carbideTiZrNbHfTaC5 in self-shielding DC arc discharge plasma[J].2022,48(3):3818-3825.]。该方法在高温熔融过程中会引起高熵金属和非金属元素组分偏析，容易形成核-边结构，对材料的结构和性能极其不利。最后，传统的无压烧结法[W.Zhang,L.Chen,C.G.Xu,et al.Densification,microstructure and mechanical properties ofmulticomponent(TiZrHfNbTaMo)C ceramic prepared by pressureless sintering[J].Journal of Materials Science&Technology,2021,72:23-28.和D.Yu,J.Yin,B.H.Zhang,et al.Pressureless sintering and properties of(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics:The effect of pyrolytic carbon[J].Journal of the European Ceramic Society,2021,41(6):3823-3831.]。
制备高熵碳化物陶瓷，一方面，传统无压烧结法均以过渡金属氧化物或者碳化物为原料，反应体系烧结活性低，导致烧结活化能较高，烧结温度高达2200-2500℃，引起晶粒异常长大；另一方面，烧结温度升高，导致晶界迁移速率增大，造成陶瓷中产生晶内闭气孔，成为后期裂纹萌生的源头。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种制备方法简单、成本低，而且元素组成和微观结构、块体尺寸可控的耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷及其制备方法。以SiB6为Si源和B源，通过碳-硼-硅化反应和固溶协同增效无压反应烧结法制备兼具优异高温抗氧化和耐烧蚀性能，且Si和B协同诱导陶瓷烧蚀后形成致密且稳定的氧化保护层
本发明的目的可以通过以下技术方案来实现：
本发明提出一种基于SiB6同时作为Si源和B源，碳-硼-硅化反应与固溶协同增效的无压反应烧结制备高熵碳化物-高熵硼化物-碳化硅复相陶瓷的方法。
具体而言，碳-硼-硅化反应与固溶协同增效的无压反应烧结法就是以SiB6为Si源和B源，纳米碳黑为C源，将碳-硼热还原反应、硅化反应与固溶反应、分步式无压烧结结合起来，通过高温反应与固溶协同促进无压烧结致密化，具体方案如下：
一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷的制备方法，该方法包括以下步骤：
(1)将过渡金属氧化物混合粉体、纳米碳黑和SiB6粉体混合，形成前躯体粉体；
(2)将前躯体粉体进行无压反应烧结，得到致密度可达96％以上的耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷。
进一步地，所述的过渡金属氧化物混合粉体中的过渡金属原子、纳米碳黑和SiB6粉体的摩尔比为(1-20):(1-64):(0-8)。优选(5-10):(12-48):(1-4)。更优选(12-16):(12-16):4。
进一步地，所述的过渡金属氧化物混合粉体为金属原子等摩尔比的HfO2、ZrO2、Ta2O5、Nb2O5和TiO2。
进一步地，所述过渡金属氧化物混合粉体的颗粒尺寸为100nm，纳米碳黑的颗粒尺寸为50nm，SiB6粉体的颗粒尺寸为3-8μm。
进一步地，步骤(1)的具体步骤为：
(1-1)将HfO2、ZrO2、Ta2O5、Nb2O5和TiO2进行球磨混合，干燥后形成过渡金属氧化物混合粉体待用；
(1-2)将过渡金属氧化物混合粉体、纳米碳黑和SiB6进行球磨混合，干燥后形成前躯体粉体。
进一步地，球磨混合时，以异丙醇为球磨介质，控制混合粉体与球石的质量比为1:(10-20)，球磨转速为200-600转/min，时间为8-60h。
进一步地，步骤(1-1)中，时间为24-60h，步骤(1-2)中，时间为8-36h。
进一步地，所述无压反应烧结的最高温度为1900-2100℃，时间为1-9h。
进一步地，所述的无压反应烧结为分步式无压反应烧结，具体升温程序为：
第一步，从室温以10-50℃/min的升温速率到1900-2100℃，保温时间为5-30min；
第二步，以50-100℃/min降温速率到1600-1900℃，保温时间为1-8h，再以10-50℃/min的降温速率降至室温，真空度控制在0.001-0.05Pa。
进一步地，无压反应烧结前，将前躯体粉体采用冷等静压预压成型圆柱坯体。
总而言之，本发明以SiB6为Si源和B源，纳米碳黑为碳源，过渡金属氧化物为相应的过渡金属源，采用碳-硼-硅化反应与固溶协同增效的无压反应烧结法可以有效制备高熵碳化物-高熵硼化物-碳化硅复相陶瓷，可以有效调控过渡金属元素种类和物相组成，进而获得高温抗氧化和耐烧蚀的高熵超高温复相陶瓷。一方面，将碳-硼-硅化反应与固溶过程结合起来，有效促进扩散传质，提高体系烧结活化能，实现高熵复相陶瓷快速烧结致密化，避免已有方法制备方法烧结温度高，晶粒异常长大的缺陷；另一方面，无压反应烧结可以适合任何形状和尺寸的高熵超高温复相陶瓷的制备，避免热压烧结和放电等离子烧结仅限于小尺寸陶瓷块体制备的缺陷。最后，一步反应烧结法实现了高熵碳化物与高熵硼化物、碳化硅陶瓷的有效复合，实现Si和B协同诱导陶瓷烧蚀氧化后形成致密且稳定的氧化层，既可以阻止氧气扩散，又可以有效抵抗机械冲刷，最终提高高熵超高温复相陶瓷的抗氧化、耐烧蚀性能。因此，本申请提供了一种不仅制备方法简单、成本低，而且元素组成和结构、块体尺寸可控的高熵碳化物-高熵硼化物-碳化硅复相陶瓷的制备方法，因此具有广阔的发展前景。
与现有技术相比，本发明具有以下优点：
(1)本发明可以实现复杂形状和大尺寸高熵超高温陶瓷的制备；
(2)本发明通过碳-硼-硅化反应和固溶降低体系反应活化能，实现较低温度下烧结致密化，避免高温、长时间烧结引起晶粒异常长大和晶内闭气孔的形成；
(3)本发明设计分步式烧结法可以实现较高温度下快速烧结致密化(致密度达到～80％)，再迅速降到较低温度进行较长时间保温，达到最终致密化，有效控制陶瓷晶粒尺寸和晶界迁移速率，进而制备结构均匀，晶粒细小且致密的高熵超高温复相陶瓷；
(4)本发明可以通过一步法实现高熵碳化物与高熵硼化物、硅基陶瓷的复合，Si和B协同诱导高熵复相陶瓷烧蚀氧化后形成富含Si和B的致密且稳定的致密氧化层，大幅度提高高熵超高温复相陶瓷的抗氧化、耐烧蚀性能；
(5)本发明的低熔点B的氧化物与挥发性气体逸出会带来“自发汗”降温机制，进一步提高高熵超高温复相陶瓷的耐烧蚀性能；
(6)本发明结合以上技术的优势，能够实现制备均匀、致密且性能优异的高熵碳化物-高熵硼化物-碳化硅高熵超高温复相陶瓷。
附图说明
图1为实施例2制备的高熵碳化物-高熵硼化物-碳化硅复相陶瓷的XRD图；
图2为实施例2制备的高熵碳化物-高熵硼化物-碳化硅复相陶瓷的SEM图；
图3为实施例2制备的高熵碳化物-高熵硼化物-碳化硅复相陶瓷的质量烧蚀率图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷及其制备方法，包括以下步骤：
(1)称取市售的过渡金属氧化物粉体(HfO2、ZrO2、Ta2O5、Nb2O5和TiO2，颗粒尺寸为～100nm，纯度≥99.0％)，以等摩尔比金属原子(nHf:nZr:nTa:nNb:nTi＝1:1:1:1:1)的过渡金属氧化物进行混合，采用行星球磨机进行混合，以异丙醇为球磨介质，控制混合粉体与球石的质量比为1:(10-20)，球磨机转速为200-600转/min，球磨24-60h后获得均匀混合的粉体，干燥后采用玛瑙研钵研磨粉体待用；
(2)分别称取一定量的上述的过渡金属氧化物混合粉体、纳米碳黑(50nm)和SiB6粉体(3-8μm)，控制过渡金属原子、纳米碳黑与SiB6的摩尔比为(1-20):(1-64):(0-8)，采用行星球磨机进行混合，以异丙醇为球磨介质，控制混合粉体与球石的质量比为1:(10-20)，球磨机转速为200-600转/min，球磨8-36h后获得均匀混合的粉体。
(3)将步骤2中的混合粉体采用冷等静压预压成型圆柱坯体，然后进行无压反应烧结过程，采用分步式烧结工艺：第一步，从室温以10-50℃/min的升温速率到1900-2100℃，保温时间为5-30min；第二步，以50-100℃/min降温速率到1600-1900℃，保温时间为1-8h，再以10-50℃/min的降温速率降至室温，真空度控制在0.001-0.05Pa，即可得到致密且均匀的高熵碳化物-高熵硼化物-碳化硅复相陶瓷，致密度可达96-100％。
以上方法中使用的过渡金属氧化物纳米粉体(HfO2、ZrO2、Ta2O5、Nb2O5和TiO2)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％；SiB6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；高温石墨烧结炉为上海晨华科技股份有限公司生产的ZT-50-22Y型真空烧结系统。
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
一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷及其制备方法，包括以下步骤：
(1)称取市售的过渡金属氧化物粉体(HfO2、ZrO2、Ta2O5、Nb2O5和TiO2，颗粒尺寸为～100nm，纯度≥99.0％)，以等摩尔比金属原子(nHf:nZr:nTa:nNb:nTi＝1:1:1:1:1)的过渡金属氧化物进行混合，采用行星球磨机进行混合，以异丙醇为球磨介质，控制混合粉体与球石的质量比为1:10，球磨机转速为500转/min，球磨24h后获得均匀混合的粉体，干燥后采用玛瑙研钵研磨粉体待用；
(2)分别称取一定量的上述的过渡金属氧化物混合粉体、纳米碳黑(50nm)和SiB6粉体(3-8μm)，控制过渡金属原子、纳米碳黑与SiB6的摩尔比为5:14:1，采用行星球磨机进行混合，以异丙醇为球磨介质，控制混合粉体与球石的质量比为1:10，球磨机转速为550转/min，球磨12h后获得均匀混合的粉体。
(3)将步骤2中的混合粉体采用冷等静压预压成型圆柱坯体，然后进行无压反应烧结过程，采用分步式烧结工艺：第一步，从室温以50℃/min的升温速率到1900℃，保温时间为30min；第二步，以100℃/min降温速率到1750℃，保温时间为7h，再以50℃/min的降温速率降至室温，真空度控制在0.001Pa，即可得到致密且均匀的高熵碳化物-高熵硼化物-碳化硅复相陶瓷，致密度可达97.5％。
实施例2
一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷及其制备方法，包括以下步骤：
(1)称取市售的过渡金属氧化物粉体(HfO2、ZrO2、Ta2O5、Nb2O5和TiO2，颗粒尺寸为～100nm，纯度≥99.0％)，以等摩尔比金属原子(nHf:nZr:nTa:nNb:nTi＝1:1:1:1:1)的过渡金属氧化物进行混合，采用行星球磨机进行混合，以异丙醇为球磨介质，控制混合粉体与球石的质量比为1:15，球磨机转速为450转/min，球磨36h后获得均匀混合的粉体，干燥后采用玛瑙研钵研磨粉体待用；
(2)分别称取一定量的上述的过渡金属氧化物混合粉体、纳米碳黑(50nm)和SiB6粉体(3-8μm)，控制过渡金属原子、纳米碳黑与SiB6的摩尔比为5:13:2，采用行星球磨机进行混合，以异丙醇为球磨介质，控制混合粉体与球石的质量比为1:15，球磨机转速为500转/min，球磨24h后获得均匀混合的粉体。
(3)将步骤2中的混合粉体采用冷等静压预压成型圆柱坯体，然后进行无压反应烧结过程，采用分步式烧结工艺：第一步，从室温以40℃/min的升温速率到1950℃，保温时间为25min；第二步，以80℃/min降温速率到1700℃，保温时间为6h，再以40℃/min的降温速率降至室温，真空度控制在0.008Pa，即可得到致密且均匀的高熵碳化物-高熵硼化物-碳化硅复相陶瓷，致密度可达98％以上。
图1中可以得出，制备的高熵超高温复相陶瓷结晶性较好，主要由两种物相组成，即(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)B2和SiC，并且主物相为(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)B2，与六方相HfB2 PDF NO.38-1398和六方相NbB2PDF NO.35-0742相对应；次物相为SiC，与立方相SiCPDF NO.29-1129相对应。
图2中可以得出，复相陶瓷结构较为致密，致密度达98.6％，晶粒尺寸为～3μm，且均匀分布，SiC均匀弥散分布于高熵硼化物中。
图3中可以得出，该复相陶瓷在2500℃的氧乙炔火焰中测试120s，质量烧蚀率为0.078mg cm-2s-1，在3000℃的氧乙炔火焰中测试120s，质量烧蚀率为-0.108mg cm-2s-1。
由此可见，采用基于SiB6作为Si源和B源的碳-硼-硅化反应和固溶协同增效无压反应烧结法制备了致密(～99％)、各物相分布均匀且晶粒尺寸较小(～3μm)的高熵碳化物-高熵硼化物-碳化硅复相陶瓷。这种方法制备高熵碳化物-高熵硼化物-碳化硅复相陶瓷结晶性较好、高熵硼化物与碳化硅均匀弥散分布于高熵碳化物中，实现Si和B协同诱导陶瓷烧蚀氧化后形成致密且稳定的氧化保护层，大大提高了高熵超高温复相陶瓷的耐烧蚀性能。这种方法制备高熵碳化物-高熵硼化物-碳化硅复相陶瓷工艺简单，烧结温度较低、操作方便，并且元素、物相组成及微观结构可控。可以一步完成制备，适合任何尺寸和复杂形状块体陶瓷的制备。这种方法制备的高熵碳化物-高熵硼化物-碳化硅复相陶瓷具有优异的耐烧蚀性能，能在2500℃的氧乙炔火焰中测试120s，质量烧蚀率仅略大于-0.05mg cm-2s-1，在3000℃的氧乙炔火焰中测试120s，质量烧蚀率不大于-0.2mg cm-2s-1，并且复相陶瓷表面无明显裂纹产生。
实施例3
一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷及其制备方法，包括以下步骤：
(1)称取市售的过渡金属氧化物粉体(HfO2、ZrO2、Ta2O5、Nb2O5和TiO2，颗粒尺寸为～100nm，纯度≥99.0％)，以等摩尔比金属原子(nHf:nZr:nTa:nNb:nTi＝1:1:1:1:1)的过渡金属氧化物进行混合，采用行星球磨机进行混合，以异丙醇为球磨介质，控制混合粉体与球石的质量比为1:20，球磨机转速为300转/min，球磨60h后获得均匀混合的粉体，干燥后采用玛瑙研钵研磨粉体待用；
(2)分别称取一定量的上述的过渡金属氧化物混合粉体、纳米碳黑(50nm)和SiB6粉体(3-8μm)，控制过渡金属原子、纳米碳黑与SiB6的摩尔比为10:32:1，采用行星球磨机进行混合，以异丙醇为球磨介质，控制混合粉体与球石的质量比为1:20，球磨机转速为300转/min，球磨36h后获得均匀混合的粉体。
(3)将步骤2中的混合粉体采用冷等静压预压成型圆柱坯体，然后进行无压反应烧结过程，采用分步式烧结工艺：第一步，从室温以20℃/min的升温速率到2000℃，保温时间为10min；第二步，以60℃/min降温速率到1900℃，保温时间为4h，再以20℃/min的降温速率降至室温，真空度控制在0.005Pa，即可得到致密且均匀的高熵碳化物-高熵硼化物-碳化硅复相陶瓷，致密度可达99％。
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。

Claims (10)

1.一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷的制备方法，其特征在于，该方法包括以下步骤：
(1)将过渡金属氧化物混合粉体、纳米碳黑和SiB6粉体混合，形成前躯体粉体；
(2)将前躯体粉体进行无压反应烧结，得到致密度可达96％以上的耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷。
2.根据权利要求1所述的一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷的制备方法，其特征在于，所述的过渡金属氧化物混合粉体中的过渡金属原子、纳米碳黑和SiB6粉体的摩尔比为(1-20):(1-64):(0-8)。
3.根据权利要求1所述的一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷的制备方法，其特征在于，所述的过渡金属氧化物混合粉体为金属原子等摩尔比的HfO2、ZrO2、Ta2O5、Nb2O5和TiO2。
4.根据权利要求1所述的一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷的制备方法，其特征在于，所述过渡金属氧化物混合粉体的颗粒尺寸为100nm，纳米碳黑的颗粒尺寸为50nm，SiB6粉体的颗粒尺寸为3-8μm。
5.根据权利要求1-4任一项所述的一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷的制备方法，其特征在于，步骤(1)的具体步骤为：
(1-1)将HfO2、ZrO2、Ta2O5、Nb2O5和TiO2进行球磨混合，干燥后形成过渡金属氧化物混合粉体待用；
(1-2)将过渡金属氧化物混合粉体、纳米碳黑和SiB6进行球磨混合，干燥后形成前躯体粉体。
6.根据权利要求5所述的一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷的制备方法，其特征在于，球磨混合时，以异丙醇为球磨介质，控制混合粉体与球石的质量比为1:(10-20)，球磨转速为200-600转/min，时间为8-60h。
7.根据权利要求1所述的一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷的制备方法，其特征在于，所述无压反应烧结的最高温度为1900-2100℃，时间为1-9h。
8.根据权利要求1或7所述的一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷的制备方法，其特征在于，所述的无压反应烧结为分步式无压反应烧结，具体升温程序为：
第一步，从室温以10-50℃/min的升温速率到1900-2100℃，保温时间为5-30min；
第二步，以50-100℃/min降温速率到1600-1900℃，保温时间为1-8h，再以10-50℃/min的降温速率降至室温，真空度控制在0.001-0.05Pa。
9.根据权利要求1所述的一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷的制备方法，其特征在于，无压反应烧结前，将前躯体粉体采用冷等静压预压成型圆柱坯体。
10.一种如权利要求1-9任一项所述方法制备的耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷。
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