CN107686356A - 一种制备超高温陶瓷基复合材料的方法 - Google Patents

一种制备超高温陶瓷基复合材料的方法 Download PDF

Info

Publication number
CN107686356A
CN107686356A CN201710785515.0A CN201710785515A CN107686356A CN 107686356 A CN107686356 A CN 107686356A CN 201710785515 A CN201710785515 A CN 201710785515A CN 107686356 A CN107686356 A CN 107686356A
Authority
CN
China
Prior art keywords
powder
zirconium
based composite
temperature ceramic
ball
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710785515.0A
Other languages
English (en)
Inventor
董航航
王操
郭强胜
赵喆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Technology
Original Assignee
Shanghai Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Technology filed Critical Shanghai Institute of Technology
Priority to CN201710785515.0A priority Critical patent/CN107686356A/zh
Publication of CN107686356A publication Critical patent/CN107686356A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
    • C04B35/58078—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3839—Refractory metal carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Abstract

本发明提供了一种制备超高温陶瓷基复合材料的方法，将氮化锆粉，碳化硼粉，无水乙醇，氧化锆小球在尼龙球磨罐中行星球磨混合均匀，把氧化锆小球过滤出来，把混合后的乙醇溶液烘干，用40目的筛网筛出细粉，在放电等离子烧结炉内进行反应烧结，在真空状态下，升温速率100℃/min，烧结温度为1600~2000℃，烧结时间为18~22分钟，其中保温时间为5~10分钟，烧结压强为50 MPa，从而在放电等离子烧结炉中通过反应烧结得到ZrB2‑ZrC超高温陶瓷基复合材料，本发明的复合材料广泛应用于固体火箭发动机的喷管喉衬、燃气舱、以及超高速飞行器的鼻锥，端头、翼前缘等耐高温结构原件的候选材料。

Description

一种制备超高温陶瓷基复合材料的方法
技术领域
本发明材料学领域，涉及一种超高温陶瓷，具体来说是一种制备超高温陶瓷基复合材料的方法。
技术背景
超高温陶瓷复合材料主要包括一些过渡金属族金属的难熔硼化物、碳化物和氮化物，如ZrB2，ZrC，HfN等，他们的熔点均在3000℃以上。在这些超高温陶瓷中，ZrB2和HfB2基超高温陶瓷复合材料具有较高的热导率、适中的热膨胀系数和良好的抗氧化烧蚀性能，可以再2000℃以上的氧化环境中实现长时间非烧蚀，是一种非常有前途的非烧蚀型超高温防热材料，可应用于载人飞行器、大气层内高超声速飞行器的鼻锥、前缘以及发动机燃烧室内关键热端部件，对提升高速飞行器气动性能、控制能力、飞行效率等方面将具有巨大贡献。
文献1（Densification of ZrB2-based composites and their mechanical andphysical properties: A review）报道硼化物，碳化物和氮化物都是高熔点的材料，硼化锆基超高温陶瓷用途比较广泛。文献2（Spark plasma sintering of ZrB2–ZrC powdermixtures synthesized by MA-SHS in air）报道硼化锆和碳化锆都有卓越的性能，比如高熔点、高强度、高热导率和化学稳定性。将硼化锆粉和碳化锆粉混合均匀在SPS中烧结可以得到相对致密的硼化锆基超高温陶瓷材料。
发明内容
针对现有技术中的上述技术问题，本发明提供了一种制备超高温陶瓷基复合材料的方法，所述的这种制备超高温陶瓷基复合材料的方法要解决现有技术中制备硼化锆-碳化锆体系超高温陶瓷基复合材料复杂的工艺，硼化锆-碳化锆体系超高温陶瓷材料的纯度不高，各相分布不均匀，影响耐高温效果的技术问题。
本发明提供了一种制备超高温陶瓷基复合材料的方法，包括如下步骤：
（1）称取氮化锆粉、碳化硼粉，其中氮化锆粉和碳化硼粉的摩尔比为3～5:1；
（2）将氮化锆和碳化硼粉放在球磨罐中，在球磨罐中加入无水乙醇，再加入氧化锆小球，放在行星球磨机上球磨2～4h，然后过滤出氧化锆小球，将浆料烘干，经筛网筛成细粉；
（3）将混合好的细粉装入石墨磨具中放在放电等离子烧结炉中烧结，压力为50MPa，在真空状态下烧结，升温速率为100℃/min，烧结温度为1600℃～2000℃，整个烧结时间为18～22分钟，其中保温时间为5～10分钟，获得超高温陶瓷基复合材料。
进一步的，所述的氮化锆粉的粒度范围为2μm，纯度为99.9%；所述的碳化硼粉的粒度为1μm，纯度为99.9%。
进一步的，所述的氮化锆粉、碳化硼粉的质量之和与无水乙醇的质量之比为1:2～4。
本发明采用反应烧结法制备，反应的方程式为：
3ZrN+B4C→2ZrB2+ZrC+3/2N2
所述反应烧结法制备硼化锆-碳化锆体系超高温陶瓷的方法，基于反应直接生成硼化锆-碳化锆体系超高温陶瓷材料。
所述的反应烧结法制备硼化锆-碳化锆体系超高温陶瓷材料的方法，
氮化锆粉的粒度范围为2μm，纯度为99.9%；碳化硼粉的粒度为1μm，纯度为99.9%。
本发明的优点及有益效果是：
1、工艺简单，成本低。本发明通过在放电等离子烧结炉中反应烧结就可以得到硼化锆-碳化锆体系的超高温陶瓷材料。
2、采用本发明获得的硼化锆-碳化锆体系的超高温陶瓷材料，纯度高，各相分布均匀，不存在其他杂质，保证合成材料具有较好的高温力学性能。
3、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、无杂质等特点，适合于作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等。
本发明和已有技术相比，其技术进步是显著的。本发明利用氮化锆和碳化硼粉体在SPS中反应烧结得到硼化锆和碳化锆体系的超高温陶瓷材料，是一种更加简单的制备硼化锆-碳化锆超高温陶瓷材料的方法，提高硼化锆-碳化锆超高温陶瓷材料的性能，提高超高温陶瓷材料的应用范围。
附图说明
图1为本发明所制备的ZrB2-ZrC复合材料的X-射线衍射图谱。
图2为本发明所制备的ZrB2-ZrC复合材料表面抛光后的扫描电镜照片。
具体实施方式
下面通过具体实施例进一步描述本发明。
实施例1
粒度为2微米，纯度为99.9%的氮化锆粉42.55克，粒度为1微米，纯度为99.9%的碳化硼粉7.45克，无水乙醇50ml，氧化锆小球150克加入到球磨罐中，行星球磨3h，过滤出球磨罐小球，将浆料放在烘箱中烘干，经过筛网晒成细粉，然后装入石墨模具中在放电等离子烧结炉中进行放电等离子烧结。在真空度≥1*10-2Pa，烧结压力为50MPa的条件下，以升温速率100℃/分钟升温到2000℃，保温5分钟，随炉冷却，即得高纯度的硼化锆-碳化锆体系超高温陶瓷材料，该体系材料可以在1800～2000oC高温下长期使用。
实施例2
粒度为2微米，纯度为99.9%的氮化锆粉42.55克，粒度为1微米，纯度为99.9%的碳化硼粉7.45克，无水乙醇50ml，氧化锆小球150克加入到球磨罐中，行星球磨3h，过滤出球磨罐小球，将浆料放在烘箱中烘干，经过筛网晒成细粉，然后装入石墨模具中在放电等离子烧结炉中进行放电等离子烧结。在真空度≥1*10-2Pa，烧结压力为50MPa的条件下，以升温速率100℃/分钟升温到1800℃，保温5分钟，随炉冷却，即得高纯度的硼化锆-碳化锆体系超高温陶瓷材料，该体系材料可以在1800～2000oC高温下长期使用。
实施例3
粒度为2微米，纯度为99.9%的氮化锆粉42.55克，粒度为1微米，纯度为99.9%的碳化硼粉7.45克，无水乙醇50ml，氧化锆小球150克加入到球磨罐中，行星球磨3h，过滤出球磨罐小球，将浆料放在烘箱中烘干，经过筛网晒成细粉，然后装入石墨模具中在放电等离子烧结炉中进行放电等离子烧结。在真空度≥1*10-2Pa，烧结压力为50MPa的条件下，以升温速率100℃/分钟升温到1600℃，保温5分钟，随炉冷却，即得高纯度的硼化锆-碳化锆体系超高温陶瓷材料，该体系材料可以在1800～2000oC高温下长期使用。

Claims (3)

1.一种制备超高温陶瓷基复合材料的方法，其特征在于包括如下步骤：
（1）称取氮化锆粉、碳化硼粉，其中氮化锆粉和碳化硼粉的摩尔比为3～5:1；
（2）将氮化锆和碳化硼粉放在球磨罐中，在球磨罐中加入无水乙醇，再加入氧化锆小球，放在行星球磨机上球磨2～4h，然后过滤出氧化锆小球，将浆料烘干，经筛网筛成细粉；
（3）将混合好的细粉装入石墨磨具中放在放电等离子烧结炉中烧结，压力为50MPa，在真空状态下烧结，升温速率为100℃/min，烧结温度为1600℃～2000℃，烧结时间为18～22分钟，保温时间为5～10分钟，获得ZrB2-ZrC超高温陶瓷基复合材料。
2.根据权利要求1所述的制备超高温陶瓷基复合材料的方法，其特征在于：所述的氮化锆粉的粒度范围为2μm，纯度为99.9%；所述的碳化硼粉的粒度为1μm，纯度为99.9%。
3.根据权利要求1所述的制备超高温陶瓷基复合材料的方法，其特征在于：所述的氮化锆粉、碳化硼粉的质量之和与无水乙醇的质量之比为1:2～4。
CN201710785515.0A 2017-09-04 2017-09-04 一种制备超高温陶瓷基复合材料的方法 Pending CN107686356A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710785515.0A CN107686356A (zh) 2017-09-04 2017-09-04 一种制备超高温陶瓷基复合材料的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710785515.0A CN107686356A (zh) 2017-09-04 2017-09-04 一种制备超高温陶瓷基复合材料的方法

Publications (1)

Publication Number Publication Date
CN107686356A true CN107686356A (zh) 2018-02-13

Family

ID=61155995

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710785515.0A Pending CN107686356A (zh) 2017-09-04 2017-09-04 一种制备超高温陶瓷基复合材料的方法

Country Status (1)

Country Link
CN (1) CN107686356A (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110627517A (zh) * 2019-10-25 2019-12-31 航天特种材料及工艺技术研究所 一种梯度超高温陶瓷基复合材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60247550A (ja) * 1984-05-23 1985-12-07 大同特殊鋼株式会社 セラミクス複合体
CN101104561A (zh) * 2007-03-16 2008-01-16 中国科学院上海硅酸盐研究所 二硼化锆基复相陶瓷的原位反应制备方法
CN101215173A (zh) * 2008-01-04 2008-07-09 中国科学院上海硅酸盐研究所 一种ZrB2－SiC－ZrC复相陶瓷材料的制备方法
CN102173813A (zh) * 2011-02-23 2011-09-07 哈尔滨工业大学 一种含硼化锆复相陶瓷材料的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60247550A (ja) * 1984-05-23 1985-12-07 大同特殊鋼株式会社 セラミクス複合体
CN101104561A (zh) * 2007-03-16 2008-01-16 中国科学院上海硅酸盐研究所 二硼化锆基复相陶瓷的原位反应制备方法
CN101215173A (zh) * 2008-01-04 2008-07-09 中国科学院上海硅酸盐研究所 一种ZrB2－SiC－ZrC复相陶瓷材料的制备方法
CN102173813A (zh) * 2011-02-23 2011-09-07 哈尔滨工业大学 一种含硼化锆复相陶瓷材料的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张翰超: "ZrN陶瓷的致密化行为及力学性能研究", 《中国优秀硕士论文全文数据库 工程科技I辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110627517A (zh) * 2019-10-25 2019-12-31 航天特种材料及工艺技术研究所 一种梯度超高温陶瓷基复合材料及其制备方法
CN110627517B (zh) * 2019-10-25 2022-03-25 航天特种材料及工艺技术研究所 一种梯度超高温陶瓷基复合材料及其制备方法

Similar Documents

Publication Publication Date Title
CN109180188B (zh) 一种高熵含硼碳化物超高温陶瓷粉体及其制备方法
CN109180189B (zh) 一种高熵碳化物超高温陶瓷粉体及其制备方法
KR102364295B1 (ko) 탄화붕소 복합재료 및 그의 제조방법
CN106478105B (zh) 一种多步反应烧结法制备低残硅的碳化硅陶瓷材料的方法
CN101215173B (zh) 一种ZrB2-SiC-ZrC复相陶瓷材料的制备方法
CN103145422B (zh) 一种碳化硼-硼化钛-碳化硅高硬陶瓷复合材料及其制备方法
CN104150940B (zh) 氮化硅与碳化硅复相多孔陶瓷及其制备方法
CN110615681A (zh) 一种多孔高熵六硼化物陶瓷及其制备方法
KR20110077154A (ko) 지르코늄디보라이드-실리콘카바이드 복합소재의 제조방법
CN107344854A (zh) 一种制备氮氧化铝透明陶瓷的方法
CN107857592A (zh) 一种高致密度超高温Ta4HfC5陶瓷块材的制备方法
KR20120072884A (ko) 지르코늄디보라이드-실리콘카바이드 복합소재 및 그 제조방법
CN107827464A (zh) 一种燃烧合成制备ZrTiCB四元陶瓷粉体的方法
CN108675795A (zh) 一种sps烧结制备高导热和高强度氮化铝陶瓷的方法
Verma et al. Effect on physical, mechanical, and wear performance of ZrB2‐based composites processed with or without additives
CN107746282A (zh) 一种原位碳化硅纤维增强液相烧结碳化硅陶瓷及制造方法
CN102674874A (zh) 一种ZrC-SiC-LaB6三元超高温陶瓷复合材料及其制备方法
CN107164803A (zh) 一种简单控制相变制备β‑氮化硅晶须的方法
CN102731096A (zh) 一种织构化硼化物基超高温陶瓷材料及其制备方法
CN107686356A (zh) 一种制备超高温陶瓷基复合材料的方法
CN105908043B (zh) 一种Mo‑ZrB2‑SiC‑AlN复合材料及其制备方法
CN106800414B (zh) 原位反应制备含氮化硼的超高温陶瓷基复合材料的方法
CN104844214B (zh) 致密化高强度碳化锆和碳化铪陶瓷材料及其低温制备方法
CN108314455A (zh) 碳化硅陶瓷及其制备方法和应用
CN100439286C (zh) 超高温近零烧蚀ZrB2－ZrC－SiC复相陶瓷的制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20180213

RJ01 Rejection of invention patent application after publication