CN117383944A - 一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷及其制备方法 - Google Patents
一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷及其制备方法，高熵陶瓷为单相面心立方结构的陶瓷，原料包括粒径为3‑5μm的TiC、粒径为2‑3μm的VC、粒径为1‑3μm的TaC、粒径为5‑10μm的NbN和粒径为5‑10μm的Cr2N；所述制备方法包括三个步骤：预合金化陶瓷粉体的制备、高熵陶瓷胚体的制备、高熵陶瓷块体的制备。本发明通过高能球磨，实现各种化合物间的初步固溶，将Cr2N转变成含有空位的CrN，有效降低了高熵陶瓷的烧结温度，有利于各种元素的扩散和均匀化，获得了单相面心立方结构的高熵陶瓷，高压力下制备胚体也使得高熵陶瓷具有较高的致密度。
Description
技术领域
本发明涉及一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷及其制备方法，属于高熵陶瓷材料制备技术领域。
背景技术
自2004年提出高熵的概念以来，不同于传统材料设计思路的高熵合金得到了迅速的发展，它将包含五种或五种以上的元素的原料以等摩尔比或近等摩尔比固溶在一起，形成单一结构的固溶体，这为新材料的研究和开发开辟了一条新的道路。随着高熵的概念应用到陶瓷领域，高熵陶瓷成为研究的热点，高熵陶瓷具有高熔点、高导热、良好的热稳定性，优异的耐蚀性和电化学性能等，具有较大发展空间和应用前景。
在现有的对高熵陶瓷的研究主要集中在单阴离子体系，对于多阴离子体系高熵陶瓷的研究尚需深入探索。另外，烧结温度高是制备高熵陶瓷所面临的一大难题，在文献“Microstructure and characterization of(Ti,V,Nb,Ta)(C,N)high-entropyceramic.”中，(Ti,V,Nb,Ta)(C,N)的制备需要在2100℃下完成，在文献“Novel refractoryhigh-entropy ceramics:Transition metal carbonitrides with superior ablationresistance.”中，(Ta0.2Hf0.2Zr0.2Ti0.2Nb0.2)C0.8N0.2的制备也需要达到2000℃，这些都是相对较高的烧结温度，因此，亟需开发出一种方法实现低温下烧结出高熵陶瓷。
发明内容
本发明为解决上述技术问题，提供一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷及其制备方法，通过高能球磨，实现各种化合物间的初步固溶，将Cr2N转变成含有空位的CrN，有效降低了高熵陶瓷的烧结温度，有利于各种元素的扩散和均匀化，制备的高熵陶瓷具有较高的致密度和优异的性能。
为解决上述技术问题，本发明所采用的技术方案是：
一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷，所述(TiCrVNbTa)(C0.66N0.33)高熵陶瓷为单相面心立方结构，原料粉末包括以下原子百分比的化合物：22.2％的TiC、22.2％的VC、22.2％的TaC、22.2％的NbN，其余的为Cr2N。
本发明技术方案的进一步改进在于：包括如下步骤：
(1)预合金化陶瓷粉体的制备：在保护气氛下，按照原料配比分别称取TiC、VC、TaC、NbN和Cr2N原料粉末放入球磨罐中，在高能球磨后，各种粉末完成初步固溶，Cr2N转变成了含有空位的CrN，获得成分均匀的陶瓷粉体混合物；
(2)高熵陶瓷胚体的制备：将步骤(1)制备的陶瓷粉体混合物放入模具中，在一定压力下保持一段时间，获得圆柱状胚体；
(3)高熵陶瓷块体的制备：将步骤(2)制备的圆柱状胚体放入导热性良好的石墨模具中，在热压烧结炉中烧结，获得(TiCrVNbTa)(C0.66N0.33)高熵陶瓷。
本发明技术方案的进一步改进在于：所述步骤(1)中原料粉末TiC的粒径为3-5μm，VC的粒径为2-3μm，TaC的粒径为1-3μm，NbN的粒径为5-10μm，Cr2N的粒径为5-10μm，并且各原料粉末的纯度均高于99.5％。
本发明技术方案的进一步改进在于：所述步骤(1)中高能球磨选用的是行星式球磨机，球磨罐和球均为玛瑙材质，球料比为10:1，球磨速度为240r/min，球磨时间为40h。
本发明技术方案的进一步改进在于：所述步骤(1)中保护气氛为氩气气氛。
本发明技术方案的进一步改进在于：所述步骤(2)中的压力为600MPa，保持时间为30min。
本发明技术方案的进一步改进在于：所述步骤(2)中在放入模具压制圆柱体之前进行过筛处理。
本发明技术方案的进一步改进在于：所述步骤(3)中将圆柱状胚体放入石墨模具中，接触内壁位置和圆柱状胚体上下表面均设置有石墨纸。
本发明技术方案的进一步改进在于：所述步骤(3)中烧结压力为30MPa，真空度低于1.8×10-2Pa。
本发明技术方案的进一步改进在于：所述步骤(3)中烧结温度为1200～1600℃，烧结过程的升温速率为10℃/min，保温时间为2h。
由于采用了上述技术方案，本发明取得的技术进步是：
本发明采用五种原料粉末TiC、VC、TaC、NbN和Cr2N，熔点分别为3140℃、2810℃、3880℃、2573℃和1650℃，通过高能球磨完成初步固溶后，生成含有较多的空位的CrN，有效降低了高熵陶瓷的烧结温度，有利于各种元素的扩散和均匀化，在1200～1600℃温度范围内成功制备出单相面心立方结构的(TiCrVNbTa)(C0.66N0.33)高熵陶瓷。
本发明制备的(TiCrVNbTa)(C0.66N0.33)高熵陶瓷具有较高的致密度，晶粒尺寸细小，熔点高，且具有良好的耐腐蚀性，相比较于原料粉体，硬度值和断裂韧性值都有显著的提高。
附图说明
图1是本发明实施例2制备的(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的XRD图谱；
图2是本发明实施例2制备的(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的SEM图；
图3是是本发明实施例2制备的(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的EDS图。
具体实施方式
下面结合实施例对本发明做进一步详细说明：
一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷为单相面心立方结构，原料粉末包括以下原子百分比的化合物：22.2％的TiC、22.2％的VC、22.2％的TaC、22.2％的NbN，其余的为Cr2N。
制备方法包括以下步骤
(1)预合金化陶瓷粉体的制备：在氩气气氛保护下，分别称取一定质量的TiC、VC、TaC、NbN和Cr2N放入行星式球磨机的球磨罐中，球料比为10:1，球磨速度为240r/min，球磨时间为40h，每球磨10h停歇1h，在高能球磨后，各种粉末完成初步固溶，Cr2N转变成了含有空位的CrN，获得成分均匀的陶瓷粉体混合物。
(2)高熵陶瓷胚体的制备：将步骤(1)制备的成分均匀的陶瓷粉体混合物过筛处理后放入模具中，在600MPa的压力下保持30min，获得圆柱状胚体。
(3)高熵陶瓷的制备：将步骤(2)制备的圆柱状胚体放入导热性良好的石墨模具中，在热压烧结炉中烧结，烧结温度为1200～1600℃，烧结过程的升温速率为10℃/min，保温时间为2h，整个烧结过程是在30MPa压力、真空度低于1.8×10-2Pa的条件下进行的。
在烧结结束后，随炉冷却至室温取出样品。
实施例1
(1)预合金化陶瓷粉体的制备：在氩气气氛保护下，分别称取2.2gTiC、2.4gVC、7.2gTaC、4.0gNbN和2.2gCr2N放入球磨罐中，球料比为10:1，球磨速度为240r/min，球磨时间为40h，每球磨10h停歇1h，在高能球磨后，各种粉末完成初步固溶，Cr2N转变成了CrN，获得成分均匀的陶瓷粉体混合物。
(2)高熵陶瓷胚体的制备：将步骤(1)制备的成分均匀的陶瓷粉体混合物过筛处理后放入模具中，在600MPa的压力下保持30min，获得圆柱状的胚体。
(3)高熵陶瓷的制备：将步骤(2)制备的圆柱状的胚体放入导热性良好的石墨模具中，在热压烧结炉中烧结，烧结温度为1400℃，烧结过程的升温速率为10℃/min，保温时间为2h，整个烧结过程是在30MPa压力下进行。
在烧结结束后，随炉冷却至室温取出样品。
烧结后的(TiCrVNbTa)(C0.66N0.33)高熵陶瓷具有优异的性能，硬度约为2086HV0.5，断裂韧性值达到6.68MPa·m1/2。
实施例2
(1)预合金化陶瓷粉体的制备：在氩气气氛保护下，分别称取2.2gTiC、2.4gVC、7.2gTaC、4.0gNbN和2.2gCr2N放入球磨罐中，球料比为10:1，球磨速度为240r/min，球磨时间为40h，每球磨10h停歇1h，在高能球磨后，各种粉末完成初步固溶，Cr2N转变成了含有空位的CrN，获得成分均匀的陶瓷粉体混合物。
(2)高熵陶瓷胚体的制备：将步骤(1)制备的成分均匀的陶瓷粉体混合物过筛处理后放入模具中，在600MPa的压力下保持30min，获得圆柱状的胚体。
(3)高熵陶瓷的制备：将步骤(2)制备的圆柱状的胚体放入导热性良好的石墨模具中，在热压烧结炉中烧结，烧结温度为1500℃，烧结过程的升温速率为10℃/min，保温时间为2h，整个烧结过程是在30MPa压力下进行。
在烧结结束后，随炉冷却至室温取出样品。
烧结后的(TiCrVNbTa)(C0.66N0.33)高熵陶瓷具有优异的性能，硬度约为2926HV0.5，断裂韧性值达到6.47MPa·m1/2。图1为(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的XRD图谱，图谱中显示了单一的面心立方结构相，没有其他相的衍射峰出现。图2为(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的SEM图，在SEM图中，样品表面没有出现明显的气孔和缺陷，表明(TiCrVNbTa)(C0.66N0.33)高熵陶瓷具有较高的致密度。图3为(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的EDS图，在EDS图中Ti、Cr、V、Nb、Ta五种元素均匀分布。
实施例3
(1)预合金化陶瓷粉体的制备：在氩气气氛保护下，分别称取2.2gTiC、2.4gVC、7.2gTaC、4.0gNbN和2.2gCr2N放入球磨罐中，球料比为10:1，球磨速度为240r/min，球磨时间为40h，每球磨10h停歇1h，在高能球磨后，各种粉末完成初步固溶，Cr2N转变成了含有空位的CrN，获得成分均匀的陶瓷粉体混合物。
(2)高熵陶瓷胚体的制备：将步骤(1)制备的成分均匀的陶瓷粉体混合物过筛处理后放入模具中，在600MPa的压力下保持30min，获得圆柱状的胚体。
(3)高熵陶瓷的制备：将步骤(2)制备的圆柱状的胚体放入导热性良好的石墨模具中，在热压烧结炉中烧结，烧结温度为1600℃，烧结过程的升温速率为10℃/min，保温时间为2h，整个烧结过程是在30MPa压力下进行。
在烧结结束后，随炉冷却至室温取出样品。
烧结后的(TiCrVNbTa)(C0.66N0.33)高熵陶瓷具有优异的性能，硬度约为2973HV0.5，断裂韧性值达到6.11MPa·m1/2，相较于1500℃下制备的高熵陶瓷，硬度值有小幅度提高，断裂韧性值降低。
以上所述的本发明优选实例主要是用来阐明本发明的制备原理和具体的实施方案，目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施。但本发明的实施方式并不限于上述的案例，在不脱离本发明的范围和精神的前提下还可做很多的修改和变化，这些变化和改进都落入要求保护的本发明的范围内。本发明要求的保护范围由所附的权利要求书及其等同物界定。
Claims (10)
1.一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷，其特征在于：所述(TiCrVNbTa)(C0.66N0.33)高熵陶瓷为单相面心立方结构，原料粉末包括以下原子百分比的化合物：22.2％的TiC、22.2％的VC、22.2％的TaC、22.2％的NbN，其余的为Cr2N。
2.根据权利要求1所述的一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的制备方法，其特征在于：包括如下步骤：
(1)预合金化陶瓷粉体的制备：在保护气氛下，按照原料配比分别称取TiC、VC、TaC、NbN和Cr2N原料粉末放入球磨罐中，在高能球磨后，各种粉末完成初步固溶，Cr2N转变成了含有空位的CrN，获得成分均匀的陶瓷粉体混合物；
(2)高熵陶瓷胚体的制备：将步骤(1)制备的陶瓷粉体混合物放入模具中，在一定压力下保持一段时间，获得圆柱状胚体；
(3)高熵陶瓷块体的制备：将步骤(2)制备的圆柱状胚体放入导热性良好的石墨模具中，在热压烧结炉中烧结，获得(TiCrVNbTa)(C0.66N0.33)高熵陶瓷。
3.根据权利要求2所述的一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的制备方法，其特征在于：所述步骤(1)中原料粉末TiC的粒径为3-5μm，VC的粒径为2-3μm，TaC的粒径为1-3μm，NbN的粒径为5-10μm，Cr2N的粒径为5-10μm，并且各原料粉末的纯度均高于99.5％。
4.根据权利要求2所述的一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的制备方法，其特征在于：所述步骤(1)中高能球磨选用的是行星式球磨机，球磨罐和球均为玛瑙材质，球料比为10:1，球磨速度为240r/min，球磨时间为40h，每球磨10h停歇1h。
5.根据权利要求2所述的一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的制备方法，其特征在于：所述步骤(1)中保护气氛为氩气气氛。
6.根据权利要求2所述的一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的制备方法，其特征在于：所述步骤(2)中的压力为600MPa，保持时间为30min。
7.根据权利要求2所述的一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的制备方法，其特征在于：所述步骤(2)中在放入模具压制圆柱体之前进行过筛处理。
8.根据权利要求2所述的一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的制备方法，其特征在于：所述步骤(3)中将圆柱状胚体放入石墨模具中，接触内壁位置和圆柱状胚体上下表面均设置有石墨纸。
9.根据权利要求2所述的一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的制备方法，其特征在于：所述步骤(3)中烧结压力为30MPa，真空度低于1.8×10-2Pa。
10.根据权利要求2所述的一种(TiCrVNbTa)(C0.66N0.33)高熵陶瓷的制备方法，其特征在于：所述步骤(3)中烧结温度为1200～1600℃，烧结过程的升温速率为10℃/min，保温时间为2h。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114605154A (zh) * | 2022-03-31 | 2022-06-10 | 大连理工大学 | 一种基于金属预合金化的高熵陶瓷材料及其制备方法 |
| CN115838291A (zh) * | 2022-10-26 | 2023-03-24 | 山东大学 | 一种采用微波快速合成高熵碳氮化物陶瓷粉体的方法 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004047A (zh) * | 2021-02-07 | 2021-06-22 | 燕山大学 | 一种(CrZrTiNbV)N高熵陶瓷块体及其制备方法 |
| CN114605154A (zh) * | 2022-03-31 | 2022-06-10 | 大连理工大学 | 一种基于金属预合金化的高熵陶瓷材料及其制备方法 |
| CN115838291A (zh) * | 2022-10-26 | 2023-03-24 | 山东大学 | 一种采用微波快速合成高熵碳氮化物陶瓷粉体的方法 |
Non-Patent Citations (1)
| Title |
|---|
| DIPPO O F，ET AL: "Bulk high-entropy nitrides and carbonitrides", 《SCIENTIFIC REPORTS》, vol. 10, no. 1, 4 December 2020 (2020-12-04) * |
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