感应等离子球化技术制备喷涂用高熵硼化物粉体

doi:10.15541/jim20250008

摘要/Abstract

摘要：

原料粉体的制备是直接影响等离子喷涂涂层结构与性能的关键技术之一。目前, 制备高熵硼化物粉体的常用方法——硼热还原法存在制备周期长、产物含杂质及用于喷涂的粉体无法直接得到等缺点。本工作采用感应等离子球化(Inductive plasma spheroidization, IPS)工艺制备了喷涂用(Zr_1/4Hf_1/4Ta_1/4Ti_1/4)B₂高熵粉体, 并与两种传统粉体制备工艺进行了比较。研究表征了不同工艺粉体的形貌、内部结构以及粒径、密度等基本性能, 探究了不同粉体制备工艺对高熵硼化物粉体显微结构及基本性能的影响, 并验证了IPS工艺制备高熵硼化物粉体的普适性。结果表明, 以商用微米级硼化物粉体为原料, 通过混合-造粒-烧结-IPS工艺可制备元素分布均匀的高熵粉体, 该粉体还具有表面光滑、球形形状、内部致密, 且松装密度和振实密度高的特征。采用IPS工艺制备不同组元种类和含量的高熵硼化物粉体, 进一步验证了该工艺具有良好的普适性。结合第一性原理计算和IPS技术的特点, 深入分析了粉体组元固溶高熵化的形成机制。本工作有望为喷涂用高熵陶瓷粉体的制备提供一种新的方法。

关键词: 感应等离子球化, 高熵陶瓷粉体, 硼化物, 喷涂用粉体

Abstract:

Fabrication of feedstock powders is a critical technology that directly influences the microstructure and performance of plasma-sprayed coatings. Conventional boron thermal reduction methods for synthesizing high-entropy boride powders encounter several limitations such as prolonged processing time, impurity contamination, and inability to obtain spray-ready powders. In this work, an inductive plasma spheroidization (IPS) process was employed to fabricate (Zr_1/4Hf_1/4Ta_1/4Ti_1/4)B₂ high-entropy powders for plasma spraying in contrast to the other two traditional powder preparation routes. The morphology, internal structure, particle size distribution, density, and other fundamental properties of powders were systematically characterized. The effects of different powder fabricating processes on the microstructure and fundamental properties of high-entropy boride powders were systematically investigated, thereby validating the broad applicability of this methodology for synthesizing high-entropy boride powders. The results demonstrate that using commercial micron-sized boride powders as precursors, a hybrid process combining mixing, spray drying, sintering with IPS facilitates the fabrication of high-entropy powders with homogeneous elemental distribution. The resulting powders exhibit spherical morphology, smooth surfaces, high internal density, and high apparent/tap density. Further experiments on synthesizing different high-entropy borides with varied compositions confirm the extensive applicability of this method. The formation mechanism of high-entropy solid solutions is elucidated through first-principles calculations combined with the unique characteristics of IPS process. This work proposes a promising method for fabricating high-entropy ceramic powders suitable for plasma-spray coatings.

Key words: inductive plasma spheroidization, high entropy ceramic powder, boride, powders for spray

中图分类号:

TQ174

余乐洋阳, 赵芳霞, 张舒心, 徐以祥, 牛亚然, 张振忠, 郑学斌. 感应等离子球化技术制备喷涂用高熵硼化物粉体[J]. 无机材料学报, 2025, 40(7): 808-816.

YU Leyangyang, ZHAO Fangxia, ZHANG Shuxin, XU Yixiang, NIU Yaran, ZHANG Zhenzhong, ZHENG Xuebin. Preparation of High-entropy Boride Powders for Plasma Spraying by Inductive Plasma Spheroidization[J]. Journal of Inorganic Materials, 2025, 40(7): 808-816.

图/表 12

图1 不同(Zr1/4Hf1/4Ta1/4Ti1/4)B2粉体的制备工艺流程图

Fig. 1 Flow chart for preparation of different (Zr1/4Hf1/4Ta1/4Ti1/4)B2 powders

表1 感应等离子球化制备粉体的工艺参数

Table 1 Process parameters for powder preparation by inductive plasma spheroidization

Parameter	Value
Second gas (H₂)/slpm	30-60
Primary gas (Ar)/slpm	120-150
Chamber pressure/psig	3-7
Powder feed rate/(g·min^-1)	20-40

图2 二元过渡金属硼化物的晶胞模型

Fig. 2 Cellular modeling of binary transition metal boride

图3 不同工艺制备的(Zr1/4Hf1/4Ta1/4Ti1/4)B2粉体的XRD图谱

Fig. 3 XRD patterns of (Zr1/4Hf1/4Ta1/4Ti1/4)B2 powders prepared by different processes

图4 MIX(a1~a4)、BTR(b1~b4)、IPS(c1~c4)粉体的SEM照片和EDS元素分布图

Fig. 4 SEM images and EDS mappings of MIX (a1-a4), BTR (b1-b4), and IPS (c1-c4) powders

表2 三种(Zr1/4Hf1/4Ta1/4Ti1/4)B2粉体的粒径分布、松装密度及振实密度

Table 2 Particle size distribution, apparent and tap densities of three kinds of (Zr1/4Hf1/4Ta1/4Ti1/4)B2 powders

Powder	D₁₀/μm	D₅₀/μm	D₉₀/μm	D₉₇/μm	Apparent density/(g·cm^-3)	Tap density/(g·cm^-3)
MIX	16.53	33.14	61.72	77.85	1.93	2.38
BTR	19.65	34.92	66.66	79.61	2.25	2.82
IPS	11.08	28.65	56.61	73.30	4.40	4.77

图5 三种工艺制备的(Zr1/4Hf1/4Ta1/4Ti1/4)B2粉体的TG-DSC曲线(a)与单组元硼化物氧化反应的吉布斯自由能(b)

Fig. 5 TG-DSC curves of (Zr1/4Hf1/4Ta1/4Ti1/4)B2 powders prepared by three processes (a) and Gibbs free energy for the oxidation reaction of single-component borides (b) Colorful figures are available on website

图6 IPS制备的(Zr1/3Nb1/3Ti1/3)B2、(Zr1/4Ta1/4Nb1/4Ti1/4)B2、(Zr1/5Cr1/5Ta1/5Nb1/5Ti1/5)B2粉体的XRD图谱

Fig. 6 XRD patterns of (Zr1/3Nb1/3Ti1/3)B2, (Zr1/4Ta1/4Nb1/4Ti1/4)B2, and (Zr1/5Cr1/5Ta1/5Nb1/5Ti1/5)B2 powders prepared by IPS

图7 IPS制备的(Zr1/3Nb1/3Ti1/3)B2 (a)、(Zr1/4Ta1/4Nb1/4Ti1/4)B2 (b)、(Zr1/5Cr1/5Ta1/5Nb1/5Ti1/5)B2 (c)粉体的SEM照片和EDS分析

Fig. 7 SEM images and EDS mappings of (Zr1/3Nb1/3Ti1/3)B2 (a), (Zr1/4Ta1/4Nb1/4Ti1/4)B2 (b), and (Zr1/5Cr1/5Ta1/5Nb1/5Ti1/5)B2 (c) powders prepared by IPS Table shows the corresponding element contents (in atom) of spot 1-spot 6

图8 感应等离子球化原理图

Fig. 8 Schematic diagram of inductive plasma spheroidization

图9 不同过渡金属Me的原子半径及基态能量

Fig. 9 Atomic radii and ground-state energies of different transition metals Me

表3 (Me0.5Zr0.5)B2的密度泛函理论能Etot和结合能Ecoh

Table 3 Density functional theory energies (Etot) and cohesive energies (Ecoh) of (Me0.5Zr0.5)B2

(Me_0.5Zr_0.5)B₂	E_tot/(eV·atom^-1)	E_coh/(eV·atom^-1)
(Ti_0.5Zr_0.5)B₂	-49.14	-7.29
(V_0.5Zr_0.5)B₂	-49.06	-7.06
(Cr_0.5Zr_0.5)B₂	-48.38	-6.62
(Nb_0.5Zr_0.5)B₂	-50.57	-7.37
(Mo_0.5Zr_0.5)B₂	-50.22	-7.07
(Hf_0.5Zr_0.5)B₂	-51.37	-7.49
(Ta_0.5Zr_0.5)B₂	-52.20	-7.59
(W_0.5Zr_0.5)B₂	-51.72	-7.32

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