粉末冶金法制备Ti<sub>4</sub>AlN<sub>3</sub>及其性能研究

郭辉; 李喜坤; 宋园园; 孙骞; 黄轶文

doi:10.7513/j.issn.1004-7638.2021.05.008

粉末冶金法制备Ti₄AlN₃及其性能研究

doi: 10.7513/j.issn.1004-7638.2021.05.008

沈阳理工大学材料科学与工程学院，辽宁沈阳 110159

基金项目: 国家自然科学基金项目（51274143）

详细信息

作者简介:
郭辉（1997—），男，内蒙古乌兰察布人，硕士研究生，主要从事先进陶瓷材料的制备、加工和应用的工作，E-mail：gentgh@163.com；

通讯作者:
李喜坤(1971—)，男，辽宁沈阳人，博士，副教授，主要从事先进陶瓷材料的制备、加工和应用的工作，E-mail：kunxi@163.com

中图分类号: TF124，TF823
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出版历程
- 收稿日期: 2021-09-09
- 刊出日期: 2021-10-30

Preparation and properties of Ti₄AlN₃ by powder metallurgy

School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110159, Liaoning, China

摘要

摘要: 采用粉末冶金法制备 Ti₄AlN₃三元层状金属陶瓷，研究不同的原料粉末、烧结温度和保温时间对其纯度的影响。利用X射线衍射仪(XRD)对烧结试样进行定性分析，并基于Rietveld法完成TOPAS定量分析，扫描电子显微镜(SEM)和能谱仪(EDS)分别表征Ti₄AlN₃的微观形貌和微区成分。结果表明，以Ti、Al和TiN 粉末为原料可以制备高纯Ti₄AlN₃块体。当保温时间为2 h、烧结温度1400 ℃时可制备出纯度较高(w_Ti₄AlN₃=98.03%)的Ti₄AlN₃陶瓷；与其他MAX相相比，Ti₄AlN₃的硬度较低，试验中随着载荷的增大，硬度值趋近于2.8 GPa。
- 金属陶瓷 /
- Ti₄AlN₃ /
- 粉末冶金法 /
- 烧结温度 /
- 保温时间 /
- 纯度 /
- 硬度
Abstract: The ternary layered cermet of Ti₄AlN₃ was prepared by powder metallurgy. The effects of raw powder, sintering temperature and holding time on the purity of Ti₄AlN₃ ceramic were studied. The samples were qualitatively analyzed by X-ray diffraction (XRD) and quantitatively analyzed by TOPAS based on Rietveld method. The microstructure and micro area composition of Ti₄AlN₃ were characterized by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The experimental results show that high purity Ti₄AlN₃ bulk can be prepared from Ti, Al and TiN powders. With the holding time of 2 h and the sintering temperature of 1 400 ℃, high purity Ti₄AlN₃ can be obtained (w_Ti₄AlN₃=98.03%). Compared with other Max phases, the hardness of Ti₄AlN₃ is lower. With the increase of load, the hardness of Ti₄AlN₃ is close to 2.8 GPa.
- ceramic /
- Ti₄AlN₃ /
- powder metallurgy method /
- sintering temperature /
- holding time /
- purity /
- hardness

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图 1 以2Ti/AlN/2TiN为原料烧结试样的XRD图谱

Figure 1. XRD pattern of the sample sintered with 2Ti/AlN/2TiN as raw material

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图 2 以Ti/Al/3TiN为原料烧结试样的XRD图谱

Figure 2. XRD pattern of the sample sintered with Ti/Al/3TiN as raw material

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图 3 不同烧结温度下试样XRD图谱

(a) 1 300 ℃；(b) 1 350 ℃；(c) 1 400 ℃；(d) 1 450 ℃；(e) 1 500 ℃

Figure 3. XRD patterns of the samples synthesized at different sintering temperatures

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图 4 不同烧结温度下Ti₄AlN₃的质量分数

Figure 4. Mass fraction of Ti₄AlN₃ at different sintering temperatures

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图 5 不同保温时间下试样XRD图谱

(a) 0.5 h；(b) 1.0 h；(c) 2.0 h；(d) 3.0 h；(e) 4.0 h

Figure 5. XRD patterns of samples with different holding time

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图 6 不同保温时间下Ti₄AlN₃的质量分数

Figure 6. Mass fraction of Ti₄AlN₃ at different holding time

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图 7 Ti/1.2Al/2.7TiN在1400 ℃下保温2 h烧结试样的断面SEM图像

Figure 7. SEM image of cross section of Ti/1.2Al/2.7TiN sintered at 1400 ℃ for 2 h

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图 8 图7中不同选区的EDS能谱

Figure 8. EDS spectra of different selected areas in Fig. 7

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图 9 维氏硬度随载荷变化曲线

Figure 9. Curve of Vickers hardness with different indentation load

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图 10 载荷为9.80 N的压痕SEM照片

Figure 10. SEM image of the indentation with load of 9.80 N

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表 1 原料粉体的相关信息

Table 1. Related information of raw powder

药品名称	平均粒径/μm	纯度/%	厂家
Ti	48	99.8	上海麦克林生化科技有限公司
Al	≤75	99.0	天津市大茂化学试剂厂
TiN	2-10	99.0	上海麦克林生化科技有限公司
AlN	2	99.5	上海麦克林生化科技有限公司

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表 2 烧结参数

Table 2. Sintering parameters

施压强度/MPa	升温速率/(℃·min⁻¹)	烧结温度/℃	保温时间/h	冷却方式
30	15	1300～1500	0.5～4	自然冷却

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表 3 图7中各微区EDS能谱分析结果

Table 3. EDS analysis results of each micro region in Fig.7

微区	y(Ti)/%	y(Al)/%	y(N)/%	化学式
谱图112	49.43	13.85	36.72	Ti_4.04Al_1.13N₃
谱图115	50.29	13.30	36.41	Ti_4.14Al_1.10N₃
谱图116	49.13	13.23	37.64	Ti_3.91Al_1.05N₃
谱图118	50.72	13.17	36.10	Ti_4.15Al_1.04N₃
平均值	49.89	13.39	36.72	Ti_4.08Al_1.09N₃

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表 4 部分MAX相的硬度值^[24-26]

Table 4. Hardness values of some MAX phases

MAX相	维氏硬度/GPa
Ti₂AlN	4.3
Nb₂AlC	6.1
Cr₂AlC	5.5
Ta₂AlC	4.4
Ti₃AlC₂	3.5
Ti₃SiC₂	4.0
Ti₃SnC₂	9.3
V₄AlC₃	6.74±0.12
β-Ta₄Al C₃	5.1

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