CN110317061B - 一种制备Al4O4C纳米纤维的方法 - Google Patents

一种制备Al4O4C纳米纤维的方法 Download PDF

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CN110317061B
CN110317061B CN201810267103.2A CN201810267103A CN110317061B CN 110317061 B CN110317061 B CN 110317061B CN 201810267103 A CN201810267103 A CN 201810267103A CN 110317061 B CN110317061 B CN 110317061B
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耿欣
温广武
肖博
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Shandong University of Technology
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Abstract

本发明提供一种Al4O4C纳米纤维的制备方法，属于纳米材料制备技术领域。其特征在于：以铝粉、氧化铝粉、石墨和钽粉为原料，按照摩尔比（1～5）：1：1：（1～3）将四者混合均匀，然后将混合粉体预制成型并将预制的坯体放置于惰性气氛炉中，向炉中通入氩气，然后以2～20℃/min的加热速度升温至1000～1600℃，保持温度0.5～5小时；然后冷却至室温即可得到超长Al4O4C纳米纤维。本发明制备的Al4O4C纳米纤维为单晶相，单根纤维中不含第二相，纳米纤维的直径分布在100‑500 nm之间，以300 nm为主，长度可达到毫米数量级，长径比>300，本发明制备工艺简单，周期短，操作安全，不造成污染。

Description

一种制备Al4O4C纳米纤维的方法
技术领域
本发明涉及一种Al4O4C纳米纤维的制备工艺，属于纳米材料制备技术领域。
背景技术
Al4O4C材料自身具有密度低、高熔点、高温稳定性优异（1890℃下能稳定存在），同时具有良好的抗氧化性和抗水化能力。因此Al4O4C是一种潜在的高性能耐火材料添加剂，应用在钢铁行业。此外，经计算Al4O4C晶体的禁带宽度为3. 8eV，被认为是一种宽带隙半导体材料。可作为高频，大功率，耐高温，抗辐射照的半导体器件及光子器件候选材料，应用在石油钻探、航空、航天等恶劣环境中。
此外，Al4O4C纳米材料处在纳米尺度；因此量子尺寸效应，小尺寸效应，表面效应等会发挥作用，使其具备以上特性外，显示新的物理性能；如Al4O4C纳米纤维在室温和低温下可以观察到光致蓝光现象；当在其晶格中掺杂约0.1 at.%的Si原子后，即可观察到从红外到紫外全色发射光谱特性，因此Al4O4C纳米纤维在白光LED的全色显示屏、场发射材料、太阳能电池、高速器件和空间器件等领域有潜在的应用。
然而，目前关于对Al4O4C纳米纤维的研究极少，关于其制备方法有以下报道：孙永的论文“One-dimensional Al4O4C ceramics: a new type of blue light emitter”采用汽-液-固法，以Al片为原料，放置在管式炉中并通入CH4和H2混合气体，加热至1310 ℃并保温2h，冷却至室温后制备出具有针状的Al4O4C纳米纤维，纤维一端连接金属Al液滴（第二相），纳米纤维长度几十微米。缺点是在高温制备过程需引入易燃易爆气体，操作危险，成本高昂；所制备的Al4O4C纳米纤维的长径比小且一端连接金属颗粒（不纯）。因此，为了解决上述缺点，制备出高长径比的Al4O4C纳米纤维，且单根纤维中不存在第二相（高纯）已至关重要。有鉴于此，特提出本发明。本发明所制备纳米纤维为Al4O4C单相材料，直径分布均匀且长度可达到毫米级。
发明内容
本发明的目的是解决原有Al4O4C材料制备难、制备工艺复杂、制备温度高、采用危险性气体、纳米纤维长度最长只能达到几微米等问题，提供一种工艺简单、操作安全、不造成污染的Al4O4C纳米纤维制备工艺，其技术方案为：以铝粉、氧化铝粉、石墨和钽粉为原料，按照摩尔比（1～5）：1：1：（1～3）将四者混合均匀，然后将混合粉体预制成型并将预制的坯体放置于惰性气氛炉中，向炉中通入氩气，然后以2～20℃/min的加热速度升温至1000～1600℃，保持温度0.5～5小时；冷却至室温后即可得到超长Al4O4C纳米纤维。
本发明的工作原理是：Al2O3-Al-C-Ta混合粉体所形成的坯体在高温加热过程中会发生以下气相-液相-固相反应：
4 Al2O3（s）+4Al（l,s）+3C（s）=3Al4O4C（s）
其中l代表液态，s代表固态和g代表气态；理论上当热处理温度高于660℃时，铝粉即发生熔化形成液相；但加入钽粉后，会形成Al-Ta合金，熔点升高；进而抑制熔融Al-Ta合金中Al的挥发。另一方面，在加热过程中会形成Al2O、AlO和CO等气相；熔融的Al-Ta合金可以通过表面吸附的形式聚集以上各种气相集团，经反应Al4O4C相在液相Al-Ta合金表面形核、长大并最终形成稳定的超长的Al4O4C纳米纤维。
本发明具有如下优点：
（1）本发明制备的Al4O4C纳米纤维，操作简单，安全可靠，不对环境造成污染；（2）本发明合成的Al4O4C纳米纤维为单晶相，纯度高（单根纤维不含第二相）；纳米纤维的直径分布在100-500 nm之间，以300 nm为主，长度达到毫米数量级，具有高长径比（>300）。
附图说明
图1是实施例1中制备的Al4O4C纳米纤维的XRD谱图。
图2是实施例1中制备的Al4O4C纳米纤维线的SEM照片。
具体实施方式
实施例1:
以铝粉、氧化铝粉、石墨和钽粉为原料，按照摩尔比1.6：1：1：2将四者混合均匀，然后将混合粉体预制成型并将预制的坯体放置于惰性气氛炉中，向炉中通入氩气，然后以5℃/min的加热速度升温至1500℃，保温1小时；然后冷却至室温即可得到超长Al4O4C纳米纤维；将制备得到的Al4O4C纳米纤维毛层揭下并对其进行X-射线衍射物相分析（XRD），测试得到的XRD谱图如图1所示。通过与Al4O4C粉末衍射卡片（PDF-01-072-1682）进行直接比对，所有的XRD峰均对应于Al4O4C相晶面，说明制备的Al4O4C纳米纤维为单相、高纯、几乎无杂质相的存在。此外，基于XRD测试结果，Al4O4C属于斜方晶系；XRD衍射峰中三强峰所对应的晶面分别对应（220）、（111）和（210）晶面族；对Al4O4C纳米纤维毛层进行扫描电子显微镜（SEM）测试，其微观形貌如图2所示。产物纯净、纳米纤维相互交织，分布均匀。平直的Al4O4C纳米纤维直径约为300 nm；长度至少为100 µm，长径比>300。
实施例2:
以铝粉、氧化铝粉、石墨和钽粉为原料，按照摩尔比1：1：1：1将四者混合均匀，然后将Al2O3-Al-C-Ta混合粉体预制成型并将预制的坯体放置于惰性气氛炉中，向炉中通入氩气，然后以2℃/min的加热速度升温至1000℃，保持温度5小时；然后冷却至室温即可得到Al4O4C纳米纤维。
实施例3:
以铝粉、氧化铝粉、石墨和钽粉为原料，按照摩尔比5：1：1：3将四者混合均匀，然后将Al2O3-Al-C-Ta混合粉体预制成型并将预制的坯体放置于惰性气氛炉中，向炉中通入氩气，然后以20℃/min的加热速度升温至1600℃，保持温度0.5小时；然后冷却至室温即可得到Al4O4C纳米纤维。

Claims (1)

1.一种制备Al4O4C纳米纤维的方法，其特征在于：以铝粉、氧化铝粉、石墨和钽粉为原料，按照摩尔比（1～5）：1：1：（1～3）将四者混合均匀，然后将混合粉体预制成型并将预制的坯体放置于惰性气氛炉中，向炉中通入氩气，然后以2～20℃/min的加热速度升温至1000～1600℃，保持温度0.5～5小时；然后冷却至室温即可得到超长Al4O4C纳米纤维。
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