CN115151358A - 基于碳化铪和碳氮化铪的超高温陶瓷材料的制造方法 - Google Patents
基于碳化铪和碳氮化铪的超高温陶瓷材料的制造方法 Download PDFInfo
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- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 27
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 16
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000011215 ultra-high-temperature ceramic Substances 0.000 title claims description 5
- 229910010293 ceramic material Inorganic materials 0.000 title abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000004137 mechanical activation Methods 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007596 consolidation process Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 2
- RGSCXUOGQGNWFC-UHFFFAOYSA-N [Hf].[C] Chemical compound [Hf].[C] RGSCXUOGQGNWFC-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 238000002490 spark plasma sintering Methods 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- -1 transition metal nitride Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
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Abstract
本发明涉及航天工程和材料科学。本文公开的本发明关于该方法的技术结果是促进和显著降低材料合成的功率和时间消耗，并且关于该材料的技术结果是提供非化学计量组成的致密陶瓷材料。所述技术结果通过提供一种基于碳化铪和碳氮化铪合成超高温材料的方法来实现，该方法包括在高能行星式球磨机中初步机械活化初始铪和碳粉末，在氩气或氮气气氛中进行自蔓延高温合成，以及随后烧结合成的混合物。使用放电等离子体烧结方法实现所述合成粉末的固结。
Description
技术领域
本发明涉及导弹和航天工程以及材料科学，更具体地，涉及基于铪(Hf)的超高温材料(Tm≥3000℃)的开发，铪可用于保护高超音速飞行器的受热影响最大的部件(吸气式发动机、鼻锥和尖锐前缘)，并且还可用于核工业。
背景技术
制造这类用于在超高温(2000℃以上)下操作的材料需要提供以下关键特性的组合：高效的除热、高抗氧化性和耐火性。从这个观点来看，最受关注的是二元和三元非化学计量化合物，更具体地，包括铪的周期表的4B和5B族过渡金属的碳化物、氮化物和碳氮化物。由于与系统中氮和/或碳量调节和主要组分的高熔点相关的困难，这些非化学计量化合物的制造是一项复杂的任务。
过渡金属氮化物的制造方法是已知的，其包括含有待氮化金属的氧化物、待氮化金属的粉末(Hf、Ti、Nb、Zr)和碱金属的叠氮化物(例如叠氮化钠)的混合物制备，由混合粉末压制坯料并在氮气气氛中使用钨丝点燃它们。该方法允许制造具有至少96％的氮化物产率和至少7.17％的氮含量的金属氮化物粉末(RU 2256604，C01B21/076，2005年7月20日)。
不能提供100％的反应产物产率和需要使用粉末及其氧化物(这导致该方法的成本增加)以及不可能改变化合物中的氮含量是该制造方法的缺点。
碳氮化钛生产方法是已知的，其包括在比例为4.5-5.1的四氯化钛和四氯乙烯混合物的镁热还原期间在氮气气氛中高温合成含钛化合物，温度范围为1010-1080℃。上述方法允许制造含钛化合物，包括具有最少量杂质的碳氮化钛(RU 2175021，C22B34/12，C22B5/04，C01B31/30，C01B21/076，2001年10月20日)。
该方法的缺点是不可能在整个组成范围内改变C/N比例，在合成的化合物中存在游离碳，需要使用还原金属，以及由于需要保持合成的高温而导致该方法的高功耗。
本文公开的材料及其制造方法的最接近的对应物是难熔金属碳化物、氮化物和碳氮化物的制造方法，其包括将难熔金属氧化物(例如HfO2、ZrO2或TiO2)与非金属材料(例如碳烟或含钙化合物CaC2、Ca3N2或CaCN2)混合，添加还原金属(钙)，在管状反应器中、在氩气气氛中和在450至800℃下合成，并且通过将形成的氧化钙CaO溶解在盐酸或乙酸中来除去形成的氧化钙CaO(RU2225837，C01B31/30，C01B21/06，B22F3/23，2004年3月20日)。
该方法的缺点是需要使用应从产物化合物中除去的还原金属氧化物，以及由于需要将管状反应器加热至450-800℃而导致的该方法的高功耗。
发明内容
本文公开的本发明的技术结果是材料合成方法的简化和显著的功率和时间消耗减少，以及制造非化学计量组成的致密陶瓷材料的可能性。
所述技术结果得以实现是通过在高能行星式球磨机中将原料Hf和C组分的混合物暴露于初步机械活化，随后对所制备的Hf和C混合物进行自蔓延高温合成并且固结所述合成的粉末。所述初步机械活化在球-混合物重量比为20：1-40：1并且行星盘速度为694-900rpm下进行5-10分钟，所述随后的自蔓延高温合成在含有氩气或氮气气氛的反应器中和在0.1-0.8MPa的压力下进行，通过白炽钨螺旋进行自持放热反应的引发，并且通过放电等离子体烧结进行合成的碳化铪(氩气)或碳氮化铪(氮气)粉末的固结，其中，在腔室中产生氩气气氛，并使1000-5000A的脉冲电流以30-70MPa的负荷通过正在烧结的样品，固结温度和暴露时间分别为1900-2200℃和2-10分钟。
具体实施方式
使用上文公开的方法制造的固结超高温材料是具有以下特性的陶瓷：
a)具有98.7％的相对密度、21.3GPa的维氏硬度和4.7MPa.m1/2的断裂韧性的HfC0.5N0.2组分的碳氮化铪；
b)具有98.5％的相对密度、10.2GPa的维氏硬度和3.6MPa.m1/2的断裂韧性的HfC0.5组分的碳化铪；
c)具有99.3％的相对密度、20.5GPa的维氏硬度和4.1MPa.m1/2的断裂韧性的HfC组分的碳化铪。
用于制造超高温氮化铪、碳化铪和碳氮化铪基陶瓷(用于保护高超音速飞行器的受热影响最大的部件)的原料组分是GFM-1级Hf金属粉末(铪粉末)(TU标准48-4-176-85(97))和P804T级C粉末(粉末碳烟)(TU标准38-1154-88)，以及氮气(GOST 9293-74)和氩气(GOST 10157-79)。
包括原料铪粉末和碳烟的研磨和混合的初步机械活化在“Activator-2S”高能行星式球磨机中进行。机械活化在具有钢球的钢小瓶中以694-900rpm的主盘速度和20：1-40：1的球-粉重量比进行5-10分钟。原料混合物的机械活化在氩气气氛中和在0.4MPa的瓶内压力下实施。机械活化导致新的非氧化表面的形成、颗粒的均匀分布和反应物之间的接触面积的增加，这反过来又加速了它们之间的反应。初步机械活化构成本文所描述方法的第一阶段。
在初步机械活化之后的本文所描述方法的第二阶段包括活化粉末或Hf+xC粉末混合物的自蔓延高温合成，其中x是从0.5至1变化的碳量，以便在实验室反应器中在氩气气氛下合成碳化铪HfCx，或者在实验室反应器中在氮气气氛下合成碳氮化铪HfCxNy。在该过程期间,实验室反应器中的气体压力为0.1-0.8MPa。
合成化合物的组分，即x和y参数，根据原料混合物中的碳量和反应器中的氮气压力而变化。
本文所描述方法的第三阶段包括非化学计量HfCx和HfCxNy粉末在放电等离子体烧结单元(放电等离子体烧结-Labox 650，SinterLand，Japan)中的固结。
放电等离子体烧结的方法基于组合暴露于高温和轴向压力，再加上具有高振幅(至5000A)的脉冲直流电流通过正在烧结的材料和包含该材料的石墨基质。脉冲电流有利于样品的均匀加热，对其微结构的影响最小。固结负荷为30-70MPa，暴露时间和烧结温度分别为2-10分钟和1900-2200℃。
每个阶段的必要部分是对经处理的样本的质量控制，其通过目视检查或用仪器方法来实施。
为了研究经合成和经固结的粉末的微结构和相组成，我们使用了扫描电子显微镜(SEM)和X射线衍射(X射线相分析)方法。对于固结的超高温非化学计量碳化铪、氮化铪和碳氮化铪基陶瓷，我们进一步控制了孔隙率、硬度、断裂韧性和微结构。
本文公开的方法的主题将进一步通过实施例来支持。
实施例1
超高温HfC0.5N0.2陶瓷的制造
将原料组分Hf和C以2：1的摩尔比(96.7重量％的Hf和3.3重量％的C)混合。将制备的原料组分的混合物在行星式球磨机中、在氩气气氛中和在0.4MPa的压力和900rpm的研磨速度下以20：1的球-粉重量比暴露于初步机械活化，以混合、研磨和清洁氧化物的粉末表面。球直径为6mm。初步机械活化的时间为10分钟。
将所得反应粉末混合物在0.8MPa的氮气压力下在反应器中暴露于自蔓延高温合成，并用白炽钨螺旋引发自持放热反应。所得碳氮化铪粉末具有HfC0.5N0.2组分。
使用放电等离子体烧结的方法固结经合成的HfC0.5N0.2粉末。为此目的，将粉末置于圆柱形石墨基质中并夹在同时用作电极的两个冲头之间，将基质置于放电等离子体烧结单元的工作空间中，在腔室中产生氩气气氛，并使脉冲电流在施加到样品上的50MPa的负荷下通过正在烧结的样品。固结温度为2000℃，暴露时间为10分钟。至烧结温度的加热速率为100℃/min。因此，样品具有圆盘形状，直径为15-50mm，厚度为2-10mm。
超高温材料具有以下参数：相对密度98.7％，维氏硬度21.3GPa，断裂韧性4.7MPa.m1/2。图1和图2示出了HfC0.5N0.2的衍射图案和微结构。
实施例2
超高温HfC0.5陶瓷的制造
将原料组分Hf和C以2：1的摩尔比(96.7重量％的Hf和3.3重量％的C)混合。将制备的原料组分的混合物在行星式球磨机中、在氩气气氛中和在0.4MPa的压力和694rpm的研磨速度下以20:1的球-粉重量比暴露于初步机械活化，以混合、研磨和清洁氧化物的粉末表面。球直径为6mm。初步机械活化的时间为5分钟。
将所得反应粉末混合物在0.8MPa的氩气压力下在反应器中暴露于自蔓延高温合成，并用白炽钨螺旋引发自持放热反应。
使用放电等离子体烧结的方法固结经合成的HfC0.5粉末。为此，将粉末置于圆柱形石墨基质中并夹在同时用作电极的两个冲头之间，将基质置于放电等离子体烧结单元的工作空间中，在腔室中产生氩气气氛，并使1000-5000A的脉冲电流在施加到样品上的70MPa的负荷下通过正在烧结的样品。固结温度为2200℃，暴露时间为10分钟。至烧结温度的加热速率为100℃/min。因此，样品具有圆盘形状，直径为15-50mm，厚度为2-10mm。
超高温HfC0.5陶瓷具有以下参数：相对密度98.5％，维氏硬度16.2GPa，断裂韧性3.6MPa.m1/2。图3和图4示出了HfC0.5的衍射图案和微结构。
实施例3
超高温HfC陶瓷的制造
将原料组分Hf和C以1：1的摩尔比(93.7重量％的Hf和6.3重量％的C)混合。将制备的原料组分的混合物在行星式球磨机中、在氩气气氛中和在0.4MPa的压力和900rpm的研磨速度下以20：1的球-粉重量比暴露于初步机械活化，以混合、研磨和清洁氧化物的粉末表面。球直径为6mm。初步机械活化的时间为5分钟。
将所得反应粉末混合物在0.4MPa的氩气压力下在反应器中暴露于自蔓延高温合成，并用白炽钨螺旋引发自持放热反应。
使用放电等离子体烧结的方法固结经合成的HfC粉末。为此目的，将粉末置于圆柱形石墨基质中并夹在同时用作电极的两个冲头之间，将基质置于放电等离子体烧结单元的工作空间中，在腔室中产生氩气气氛，并使脉冲电流以施加到样品的30MPa的负荷通过正在烧结的样品。固结温度为1900℃，暴露时间为10分钟。至烧结温度的加热速率为100℃/min。因此，样品具有圆盘形状，直径为15-50mm，厚度为2-10mm。
超高温陶瓷具有以下参数：相对密度99.3％，维氏硬度20.5GPa，断裂韧性4.1MPa.m1/2。图5和图6示出了HfC的衍射图案和微结构。
Claims (1)
1.一种基于碳化铪或碳氮化铪超高温陶瓷制造方法的超高温陶瓷制造方法，包括在高能行星式球磨机中对Hf和C原料组分混合物进行初步机械活化，随后对制备的Hf和C混合物进行自蔓延高温合成并且固结所述合成的粉末，其中所述初步机械活化在球-粉重量比为20：1-40：1且主盘速度为694-900rpm下实施5-10分钟，所述随后的自蔓延高温合成在具有氩气或氮气气氛的反应器中和在0.1-0.8MPa的压力下进行，用白炽钨螺旋引发自持放热反应，并通过放电等离子体烧结使合成的碳化铪或碳氮化铪粉末固结，进一步地，其中在反应室中产生氩气气氛，并使1000-5000A的脉冲电流以30-70MPa的负荷通过正在烧结的样品，所述固结温度和暴露时间分别为1900-2200℃和2-10分钟。
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| WO2021133226A1 (en) | 2021-07-01 |
| RU2729277C1 (ru) | 2020-08-05 |
| CN115151358B (zh) | 2024-05-24 |
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