CN117430423A - 一种碳空位高熵碳化物(TiVNbMoW)Cx的制备方法 - Google Patents
一种碳空位高熵碳化物(TiVNbMoW)Cx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 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 39
- 239000000919 ceramic Substances 0.000 claims abstract description 33
- 239000011812 mixed powder Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 229910052786 argon Inorganic materials 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 21
- 238000007254 oxidation reaction Methods 0.000 abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 150000001247 metal acetylides Chemical class 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种碳空位高熵碳化物(TiVNbMoW)Cx的制备方法，是以Ti粉、V粉、Nb粉、Mo粉、W粉和碳粉作为原料，混合后加入少量乙醇，在氩气保护气氛中研磨得到混合粉末；再将所得混合粉末干燥后压制成型得到生坯，然后将生坯进行放电等离子烧结，自然冷却至室温，得到高熵碳化物陶瓷(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx(0.7≤x＜1)。本发明通过控制碳的用量和制备工艺巧妙的在高熵碳化物中引入碳空位，而含有大量的碳空位会优先吸附氧气生成碳质氧化物，碳质氧化物可以阻止氧气向内部扩散进而改善抗氧化性能，进而有效改善了高熵碳化物抗氧化性能。
Description
技术领域
本发明属于高熵化合物制备技术领域，涉及一种高熵碳化物的制备方法，尤其涉及一种碳空位高熵碳化物(TiVNbMoW)Cx的制备方法，以提高高熵碳化物的抗氧化性能，从而拓展高熵碳化物的应用。
背景技术
高熵合金具有不少于五种主要金属元素组成，每种金属成分为等摩尔比或近等摩尔比。受高熵合金的启示，激发了对高熵陶瓷的研究。高熵陶瓷是一种新型的单相陶瓷。目前主要包括碳化物，氧化物，氮化物，二硼化物等。高熵碳化物（HECs）主要是由 IVB-VIB 族过渡金属碳化物组成的固溶体，因其超高的熔点、良好的热稳定性、耐高温蠕变性和抗辐照性而备受关注。高熵碳化物一般具有等金属摩尔比和非碳化学计量偏差。最近，研究人员报道了存在碳空位的非等金属摩尔比的高熵碳化物。同时，由于典型的面心立方结构，含有碳空位的高熵碳化物仍能以稳定的形式存在。以往的许多研究都表明，碳空位的存在有利于降低高熵碳化物的烧结温度和热导率。同时，碳空位也有利于提高硬度，杨氏模量和抗弯强度。然而高熵碳化物由于具有超高的熔点（>3000℃）往往使用在高温环境下。高熵碳化物的抗氧化性能限制了其使用。因此提高高熵碳化物的抗氧化性能具有重要意义。
发明内容
本发明的目在于提供一种碳空位高熵碳化物(TiVNbMoW)Cx的制备方法。
一、碳空位高熵碳化物(TiVNbMoW)Cx的制备
本发明碳空位高熵碳化物的制备方法，包括以下步骤：
（1）取Ti粉、V粉、Nb粉、Mo粉、W粉和碳粉作为原料，混合后加入少量乙醇，在氩气保护气氛中研磨得到混合粉末。
原料Ti粉、V粉、Nb粉、Mo粉、W粉和C粉的纯度均≥99%，粒径均<10μm。Ti、V、Nb、Mo、W和C的摩尔比为1:1:1:1:1:（3.5~5）。
研磨中，研磨球与原料的质量比为3:1~10:1，球磨机的转速为200~800 r/min；球磨时间为3~20 h。
（2）将所得混合粉末干燥后用液压机在30MPa下压制成型得到生坯，然后将生坯进行放电等离子烧结，自然冷却至室温，得到高熵碳化物陶瓷(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx。
烧结工艺对高熵碳化物陶瓷的结构和性能有很大的影响。烧结温度较低，保温时间过短，压力较小不容易合成高熵碳化物陶瓷(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx，而烧结温度较高，保温时间过长，压力较大使得晶粒生长较大，导致其力学性能较差。因此本发明在放电等离子烧的工艺过程为：升温速率为20~300 ℃/min，烧结温度为1800~2300℃，保温时间为0.1~1 h，压力为1.5~30 MPa，真空度＜101Pa。
本发明通过控制碳的用量和制备工艺巧妙的在高熵碳化物中引入碳空位，所制备的高熵碳化物陶瓷(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx中(0.7≤x＜1)。
图1为本发明制备的高熵碳化物(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx陶瓷的XRD图谱。XRD图谱显示，所制备的高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx高熵陶瓷为纯相，未含有其他杂质相。
图2 为本发明制备的高熵碳化物(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx陶瓷抛光表面的SEM图像以及相应的EDS元素分布图。SEM图和EDS元素分布图显示，所制备的(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx陶瓷中五种组成元素大致均匀分布。
二、碳空位高熵碳化物(TiVNbMoW)Cx的抗氧化性能
测试方法：首先把高熵碳化物(TiVNbMoW)Cx块体用粉碎机粉碎并筛选成粉末。HE-TMCx粉末的抗氧化性在热重分析仪中进行，空气中的加热速度为 10 ℃/min,加热至1000℃停止加热然后自然冷却。为了说明碳空位高熵碳化物(TiVNbMoW)Cx的抗氧化性能的提高，本实验与常规的高熵碳化物(TiVNbMoW)C进行比较。
图3为高熵碳化物(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx的TG曲线。通过热重测试在室温-1000℃的氧化区间内，高熵碳化物(TiVNbMoW)C的TG曲线最先发生质量变化，说明最先发生了氧化。高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.7陶瓷展现了最为优异的抗氧化性能。同时，相比于陶瓷(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.8和(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.9，高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.7的初始氧化温度最高，增重率最低（25.2%），氧化速度也最低（0.1577%/℃）。
图4为高熵碳化物(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx的DSC曲线。从图中可得，高熵碳化物(Ti0.2V0.2Nb0.2Mo0.2W0.2)C和(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.7最先开始放热反应，高熵碳化物(Ti0.2V0.2Nb0.2Mo0.2W0.2)C由于具有多余的碳，而高熵碳化物(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.7由于含有大量的碳空位会优先吸附氧气生成碳质氧化物，碳质氧化物可以阻止氧气向内部扩散进而改善抗氧化性能。
附图说明
图1为高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx陶瓷的XRD图谱。
图2为高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx抛光表面的SEM图像以及相应的EDS元素分布图。
图3为高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx的TG曲线。
图4为高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx的DSC曲线。
具体实施方式
以下结合具体实施例及附图对本发明碳空位高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx陶瓷的制备及性能进行详细说明。
实施例1、高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.7陶瓷的制备
（1）以Ti、V、Nb、Mo、W和C粉粉末按1:1:1:1:1:3.5的摩尔比配料，加入少量乙醇，置于碳化钨球磨罐中（碳化钨球:混合粉=5:1）；将该球磨罐置于球磨机中以200 r/min的转速球磨8 h得到混合粉体；
（2）将步骤（1）中得到的混合粉体干燥后，用液压机在30MPa下进行预压制成型得到生坯，然后将生坯进行放电等离子烧结。放电等离子烧结工艺条件：对气氛炉进行抽真空处理，使真空示数数值＜101Pa，之后以100 ℃/min的升温速率将炉温从室温升至2150 ℃，保温10min；随后关闭电源自然冷却至室温，得到(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.7高熵陶瓷。XRD图谱（图1）表明，所制备的(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.7高熵陶瓷为纯相，未含有其他杂质相；SEM图以及元素分布图显示，合成的高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.7陶瓷五种组成元素大致均匀分布；
（3）高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.7陶瓷的抗氧化性能：氧化速度0.1577%/℃，增重率25.2%。
实施例2、高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.8陶瓷的制备
（1）以Ti、V、Nb、Mo、W和C粉粉末按1:1:1:1:1:4的摩尔比配料，加入少量乙醇，置于碳化钨球磨罐中（碳化钨球:混合粉=5:1）；将该球磨罐置于球磨机中以300 r/min的转速球磨5 h得到混合粉体；
（2）将步骤（1）中得到的混合粉体干燥后，用液压机在30MPa下进行预压制成型得到生坯，然后将生坯进行放电等离子烧结。放电等离子烧结工艺条件：对气氛炉进行抽真空处理，使真空示数数值＜100Pa，之后以150 ℃/min的升温速率将炉温从室温升至2200 ℃，保温5min；随后关闭电源自然冷却至室温，得到(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.8高熵陶瓷。XRD图谱（图1）表明，所制备的(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.8高熵陶瓷为纯相，未含有其他杂质相；SEM图以及元素分布图显示，合成的高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.8陶瓷五种组成元素大致均匀分布；
（3）高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.8陶瓷的抗氧化性能：氧化速度0.1586%/℃，增重率29.4%。
实施例3、高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.9陶瓷的制备
（1）以Ti、V、Nb、Mo、W和C粉粉末按1:1:1:1:1:4.5的摩尔比配料，加入少量乙醇，置于碳化钨球磨罐中（碳化钨球:混合粉=3:1）；将该球磨罐置于球磨机中以400 r/min的转速球磨9h得到混合粉体；
（2）将步骤（1）中得到的混合粉体干燥后，用液压机在30MPa下进行预压制成型得到生坯，然后将生坯进行放电等离子烧结。放电等离子烧结工艺条件：对气氛炉进行抽真空处理，使真空示数数值＜100Pa，之后以100 ℃/min的升温速率将炉温从室温升至2300 ℃，保温10min；随后关闭电源自然冷却至室温，得到(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.9高熵陶瓷。XRD图谱（图1）表明，所制备的(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.7高熵陶瓷为纯相，未含有其他杂质相；SEM图以及元素分布图显示，合成的高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.7陶瓷五种组成元素大致均匀分布（图2）；
（3）高熵(Ti0.2V0.2Nb0.2Mo0.2W0.2)C0.9陶瓷的抗氧化性能：氧化速度0.1929%/℃，增重率26.2%。
上述各实施例中，采用的Ti粉、V粉、Nb粉、Mo粉、W粉和C粉的纯度均≥99 %，粒径均<10μm。
Claims (3)
1.一种碳空位高熵碳化物(TiVNbMoW)Cx的制备方法，包括以下步骤：
（1）取Ti粉、V粉、Nb粉、Mo粉、W粉和碳粉作为原料，混合后加入少量乙醇，在氩气保护气氛中研磨得到混合粉末；所述Ti、V、Nb、Mo、W和C的摩尔比为1:1:1:1:1:（3.5~5；
（2）将所得混合粉末干燥后用液压机在30MPa下压制成型得到生坯，然后将生坯进行放电等离子烧结，自然冷却至室温，得到高熵碳化物陶瓷(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx；所述放电等离子烧的工艺条件为：升温速率为20~300 ℃/min，烧结温度为1800~2300℃，保温时间为0.1~1 h，压力为1.5~30 MPa，真空度＜101 Pa；所制备的高熵碳化物陶瓷(Ti0.2V0.2Nb0.2Mo0.2W0.2)Cx中，0.7≤x＜1。
2.如权利要求1所述一种碳空位高熵碳化物(TiVNbMoW)Cx的制备方法，其特征在于：原料Ti粉、V粉、Nb粉、Mo粉、W粉和C粉的纯度均≥99%，粒径均<10μm。
3.如权利要求1所述一种碳空位高熵碳化物(TiVNbMoW)Cx的制备方法，其特征在于：研磨中，研磨球与原料的质量比为3:1~10:1，球磨机的转速为200~800 r/min；球磨时间为3~20 h。
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