CN108560058B - 一种碳化锆晶须的制备方法 - Google Patents
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- 229910026551 ZrC Inorganic materials 0.000 title claims abstract description 41
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000011302 mesophase pitch Substances 0.000 claims abstract description 28
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000010574 gas phase reaction Methods 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010426 asphalt Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 3
- 239000011824 nuclear material Substances 0.000 abstract description 3
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000011295 pitch Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/005—Growth of whiskers or needles
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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Abstract
一种碳化锆晶须的制备方法，本发明利用中间相沥青和四氯化锆反应物在高温下，中间相沥青和四氯化锆的质量比为1:10–10:1，把中间相沥青制粉，粒度为5‑2000目，再在惰性无水气氛下和四氯化锆粉末混合，研磨2‑5h，在真空或惰性气氛下分三个温度段加热至1200‑1500℃，发生分解、挥发和气相反应，生成的碳化锆晶须沉积在基体表面，碳化锆晶须直径在50nm‑100μm，长度为0.5‑1.5mm。本发明可以在不使用催化剂的条件下大面积生长碳化锆晶须。生长的碳化硅晶须纯度高、品质好，在超高温材料、核材料和电子零部件上的应用具有前景。
Description
技术领域
本发明涉及一种碳化锆晶须制备方法。
背景技术
碳化锆晶须是陶瓷晶须的一种，由于自身具有高强度、耐高温、高硬度和良好的导热、导电性能，在高温陶瓷领域、核材料领域和电极材料领域有着可期的应用前景。目前制备碳化锆晶须的方法较少，常规方法制备陶瓷晶须通常需要引入催化剂，催化剂的残留往往会影响陶瓷晶须的纯度和质量，而高温陶瓷和电极材料领域往往需要高质量的碳化锆晶须，其中最重要的标准就是晶须的纯度和均匀性。引入生产制备均匀性好纯度高的碳化锆晶须材料成为相关领域的技术瓶颈。碳化锆的纯度可以通过选择替代催化剂生长的技术来解决，化学气相生长技术可以制备多种结构的陶瓷晶须，是生长制备高纯碳化锆晶须的首选方法。另外，碳化锆晶须的均匀性问题可以通过控制化学气相沉积的工艺条件得到解决。
发明内容
本发明的目的在于提供一种用于大批量制备高纯碳化锆晶须材料的方法，采用中间相沥青作为碳源、四氯化锆作为锆源，利用等温等压化学气相沉积法制备均匀性好纯度高的碳化锆晶须，通过控制四氯化锆和中间相沥青的比例，在加热炉内，惰性气氛或真空下生长碳化锆晶须。
本发明一种碳化锆晶须的制备方法，制备工艺如下：
利用中间相沥青作为碳源，沥青的灰分小于100ppm，软化点100-300℃，H/C为0.32-0.68；利用四氯化锆作为锆源，中间相沥青和四氯化锆的质量比为1:10-10:1，惰性无水气氛下混合研磨2-5h。在真空或惰性气氛下分三个阶段加热至1200-1500℃，充分发生分解、挥发和气相反应，并沉积在基体表面生成碳化锆晶须。制备的碳化锆晶须直径在50nm-100μm，长度在0.5-1.5mm。
所述的中间相沥青是合成中间沥青、油系中间沥青或煤系中间沥青。
所述在真空或惰性气氛下加热至1200-1500℃，升温反应分成三个阶段，第一阶段由室温升至沥青软化点温度，保温30min；第二阶段由沥青软化点温度缓慢升至450℃，升温速率低于2℃/min，此阶段中间相沥青开始分解；第三阶段快速升温至1200-1500℃，升温速率5-10℃/min，并自然冷却至室温，四氯化锆大量挥发并和沥青的分解产物反应生成碳化锆晶须，沉积在基体上。
所述的基体为陶瓷、石墨、碳/碳复合材料或碳纤维。
本发明利用化学气相沉积在不引入催化剂的条件下，生长制备出均匀的碳化锆晶须，生长的碳化硅晶须纯度高、品质好，在超高温材料、核材料和电子零部件上的应用具有前景，采用分阶段升温，有效实现了碳化锆晶须的结构和性能优化。
附图说明
图1为本发明实施例1制备的制备ZrC晶须图。
具体实施方式
以下结合附图和具体实施方式对本发明做进一步的描述。
实施例1
利用中间相沥青作为碳源，沥青的灰分为100ppm，软化点为160℃，H/C为0.66；利用四氯化锆作为锆源，中间相沥青和四氯化锆的质量比为1:2，惰性、无水气氛下混合研磨5h。在真空或惰性气氛下分三个阶段加热至1500℃，第一阶段由室温升至160℃，保温30min；第二阶段由160℃缓慢升至450℃，升温速率为2℃/min；第三阶段快速升温至1500℃，升温速率10℃/min，并自然冷却至室温，四氯化锆大量挥发并和沥青的分解产物反应生成碳化锆晶须，沉积在基体上。充分发生分解、挥发和气相反应，并沉积在石墨基体表面生成碳化锆晶须，其形貌图如图1所示。
实施例2
利用中间相沥青作为碳源，沥青的灰分为70ppm，软化点为260℃，H/C为0.56；利用四氯化锆作为锆源，中间相沥青和四氯化锆的质量比为1:8，惰性、无水气氛下混合研磨3h。在真空或惰性气氛下分三个阶段加热至1350℃，第一阶段由室温升至260℃，保温30min；第二阶段由260℃缓慢升至450℃，升温速率为1℃/min；第三阶段快速升温至1350℃，升温速率7℃/min，并自然冷却至室温，四氯化锆大量挥发并和沥青的分解产物反应生成碳化锆晶须，沉积在基体上。充分发生分解、挥发和气相反应，并沉积在碳纤维基体表面生成碳化锆晶须。
实施例3
利用中间相沥青作为碳源，沥青的灰分为40ppm，软化点为300℃，H/C为0.52；利用四氯化锆作为锆源，中间相沥青和四氯化锆的质量比为4:1，惰性、无水气氛下混合研磨2h。在真空或惰性气氛下分三个阶段加热至1200℃，第一阶段由室温升至300℃，保温30min；第二阶段由300℃缓慢升至450℃，升温速率为0.7℃/min；第三阶段快速升温至1200℃，升温速率5℃/min，并自然冷却至室温，四氯化锆大量挥发并和沥青的分解产物反应生成碳化锆晶须，沉积在基体上。充分发生分解、挥发和气相反应，并沉积在炭炭复合材料基体表面生成碳化锆晶须。
Claims (4)
1.一种碳化锆晶须的制备方法，其特征在于：利用中间相沥青作为碳源，中间相沥青的灰分小于100ppm，软化点100-300℃，H/C为0.32-0.68；利用四氯化锆作为锆源，中间相沥青和四氯化锆的质量比为1:10–10:1，把中间相沥青制粉，粒度为5-2000目，再在惰性无水气氛下和四氯化锆粉末混合，研磨2-5h，在真空或惰性气氛下分三个温度段加热至1200-1500℃，发生分解、挥发和气相反应，生成的碳化锆晶须沉积在基体表面，碳化锆晶须直径在50nm-100μm，长度为0.5-1.5mm。
2.根据权利要求1所述的碳化锆晶须的制备方法，其特征在于：所述的中间相沥青是合成中间沥青、油系中间沥青或煤系中间沥青。
3.根据权利要求1或2所述的碳化锆晶须的制备方法，其特征在于：所述的在真空或惰性气氛下加热至1200-1500℃，加热升温反应分成三个阶段，第一阶段由室温升至沥青软化点温度，保温30min；第二阶段由沥青软化点温度缓慢升至450℃，升温速率低于2℃/min，中间相沥青开始分解；第三阶段快速升温至1200-1500℃，升温速率5-10℃/min，并自然冷却至室温，四氯化锆大量挥发并和沥青的分解产物反应生成碳化锆晶须，沉积在基体上。
4.根据权利要求1所述的碳化锆晶须的制备方法，其特征在于：基体为陶瓷、石墨、碳/碳复合材料或碳纤维。
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| CN114032607B (zh) * | 2021-11-02 | 2024-01-09 | 西北工业大学 | 一种采用碳化锆籽晶制备碳化锆晶须的方法 |
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