激光诱导方钴矿自蔓延高温合成过程研究

doi:10.15541/jim20220714

无机材料学报 ›› 2023, Vol. 38 ›› Issue (7): 815-822.DOI: 10.15541/jim20220714 CSTR: 32189.14.10.15541/jim20220714

激光诱导方钴矿自蔓延高温合成过程研究

姚磊(), 杨东旺(), 鄢永高, 唐新峰()

武汉理工大学材料复合新技术国家重点实验室, 武汉 430070

收稿日期:2022-11-28 修回日期:2023-01-04 出版日期:2023-01-11 网络出版日期:2023-01-11
通讯作者: 杨东旺, 助理研究员. E-mail: ydongwang@whut.edu.cn;
唐新峰, 教授. E-mail: tangxf@whut.edu.cn
作者简介:姚磊(1989-), 男, 博士研究生. E-mail: yaolei1644@whut.edu.cn
基金资助:
中央高校基本科研项目(WUT 2017-YB-013)

Laser-induced Self-propagating High-temperature Synthesis of Skutterudite

YAO Lei(), YANG Dongwang(), YAN Yonggao, TANG Xinfeng()

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China

Received:2022-11-28 Revised:2023-01-04 Published:2023-01-11 Online:2023-01-11
Contact: YANG Dongwang, research assistant. E-mail: ydongwang@whut.edu.cn;
TANG Xinfeng, professor. E-mail: tangxf@whut.edu.cn
About author:YAO Lei (1989-), male, PhD candidate. E-mail: yaolei1644@whut.edu.cn
Supported by:
Fundamental Research Funds for the Central Universities(WUT 2017-YB-013)

摘要/Abstract

摘要：

通过自蔓延高温合成(SHS)及其衍生方法可以超快速地制备热电材料粉体或块体, 并获得优异的热电性能。但是在采用SHS技术制备方钴矿材料的过程中, 易出现非稳态SHS反应, 使得反应后的坯体中产生杂相。本工作采用激光诱导点火和坯体预热相结合的方法, 分别研究了激光点火的功率密度η和预热温度T₀对方钴矿材料自蔓延高温合成过程的影响, 总结了方钴矿CoSb₃燃烧模式的变化规律, 并获得了制备单相的工艺窗口。研究结果表明, 当激光点火功率密度η固定时, 随着预热温度T₀升高, 方钴矿的SHS反应存在“反应中止→非稳态螺旋燃烧→稳态燃烧→非稳态螺旋燃烧”的转变过程; 在η=3.75 J·mm^-2, 250 ℃≤T₀<370 ℃条件下, 可以获得单相CoSb₃。

关键词: 自蔓延高温合成, 方钴矿, 包晶反应, 稳态燃烧

Abstract:

High performance thermoelectric powders or bulks can be quickly obtained by self-propagating high- temperature synthesis (SHS) or its derivative methods. In the process of preparing skutterudite by SHS technology, unsteady SHS reaction is easy to occur, which leads to impurity phase in the powders compact after reaction. In this work, the SHS process of the skutterudite was investigated via regulating the power density of the laser (η) and preheating temperature (T₀) by laser induction and preheating of powders compact, respectively. The change of combustion mode for the skutterudite of CoSb₃ was observed and the process window for single phase was obtained. As a result, with fixed η and increased T₀, the state of the SHS process changes correspondingly, i.e., reaction stop→unsteady spiral combustion→steady-state combustion→unsteady spiral combustion. With η=3.75 J·mm^-2 and 250 ℃≤T₀<370 ℃, the single-phase of CoSb₃ can be obtained successfully.

Key words: self-propagating high-temperature synthesis, skutterudite, peritectic reaction, steady-state combustion

中图分类号:

TQ174

姚磊, 杨东旺, 鄢永高, 唐新峰. 激光诱导方钴矿自蔓延高温合成过程研究[J]. 无机材料学报, 2023, 38(7): 815-822.

YAO Lei, YANG Dongwang, YAN Yonggao, TANG Xinfeng. Laser-induced Self-propagating High-temperature Synthesis of Skutterudite[J]. Journal of Inorganic Materials, 2023, 38(7): 815-822.

图/表 13

图1 室温条件下激光诱导方钴矿SHS反应过程

Fig. 1 Laser-induced skutterudite SHS reaction process at room temperature (a-c) I. SHS processes and II. time-dependent temperature curves of sample RT6.25, RT12.5 and RT25, respectively; (d) Section photographs of RT6.25, RT12.5 and RT25; (e, f) XRD patterns of powders in (e) porous and (f) dense areas

图2 (a)室温和预热SHS实验设备示意图; (b)预热模块的实物图; (c~h)样品Px(x=150, 200, 250, 300, 350, 400)的I. 燃烧波前沿(t=0.95 s)和II. SHS实验后坯体截面照片; (i)CoSb3体系中燃烧温度和燃烧速度随激光点火功率密度变化的趋势

Fig. 2 (a) Schematic diagram of room temperature and preheating SHS experiment; (b) Physical picture of the preheating module; (c-h) I. combustion wave front (t=0.95 s) and II. section photographs of powders compacts after SHS for sample Px(x=150, 200, 250, 300, 350, 400); (i) Trend graph of combustion temperature and combustion velocity changed with power density of ignition laser in CoSb3 system

图3 不同预热温度时CoSb3体系中四种典型SHS反应现象

Fig. 3 Four typical SHS performances in CoSb3 system with different preheating temperatures (a) T0=150 ℃; (b) T0=160 ℃; (c) T0=300 ℃; (d) T0=400 ℃

图4 (a) CoSb3体系中燃烧温度随预热温度变化趋势图和(b)区域3附近燃烧速率的变化趋势

Fig. 4 (a) Trend graph of combustion temperature changed with preheating temperature in CoSb3 system and (b) variation trend of combustion rate around region 3

图5 不同预热温度区间SHS实验后坯体粉末的XRD谱图

Fig. 5 XRD patterns of compact powders after SHS in different preheating temperature ranges (a) T0≤150 ℃; (b) 150 ℃<T0<250 ℃; (c) 250 ℃≤T0<370 ℃; (d) T0≥370 ℃

图S1 SHS装置示意图

Fig. S1 Schematic diagram of the SHS device

表S1 室温自蔓延样品的激光点火工艺参数

Table S1 Laser ignition process for SHS samples at room temperature

Sample	Ignition time, t/s	Laser power, P/W	Scan rate, v_L/ (mm·s^-1)	Scan spacing, d/mm	Energy density, η/(J·mm^-2)
RT6.25	0.81	500	800	0.10	6.25
RT12.5	1.31	500	400	0.10	12.5
RT25	2.56	500	400	0.05	25

图S2 样品RT6.25、RT12.5和RT25的XRD谱图

Fig. S2 XRD patterns of samples RT6.25, RT12.5 and RT25

表S2 预热状态下自蔓延样品的激光点火工艺参数

Table S2 Laser ignition process of SHS samples under preheating condition

Sample	Preheating temperature, T/℃	Ignition time, t/s	Laser power, P/W	Energy density, η/(J·mm^-2)	Sample	Preheating temperature, T/℃	Ignition time, t/s	Laser power, P/W	Energy density, η/(J·mm^-2)
P150	300	0.95	150	1.88	T210	210	0.95	300	3.75
P200	300	0.95	200	2.50	T220	220	0.95	300	3.75
P250	300	0.95	250	3.13	T230	230	0.95	300	3.75
P300	300	0.95	300	3.75	T240	240	0.95	300	3.75
P350	300	0.95	350	4.38	T250	250	0.95	300	3.75
P400	300	0.95	400	5.00	T330	330	0.95	300	3.75
T150	150	0.95	300	3.75	T350	350	0.95	300	3.75
T160	160	0.95	300	3.75	T380	380	0.95	300	3.75
T170	170	0.95	300	3.75	T400	400	0.95	300	3.75
T200	200	0.95	300	3.75

图S3 样品Px在热电偶TC1(黑色)和TC2(红色)处温度随时间的变化关系曲线

Fig. S3 Time-dependent temperature graphs of sample Px at the thermocouple TC1 (black) and TC2 (red)

图S4 样品Tx(x=150, 160, 300, 400)在热电偶TC1(黑色)和TC2(红色)处温度随时间的变化关系曲线

Fig. S4 Time-dependent temperature graphs of sample Tx(x=150, 160, 170, 200, 210, 220, 230, 240, 250, 330, 350, 380, 400) at the thermocouple TC1 (black) and TC2 (red)

图S5 (a, b)样品P300和(c, d)样品T400的二次电子像、背散射电子像((a, c)×200, (b, d) ×5000)

Fig. S5 SE, BSE images ((a, c)×200, (b, d) ×5000) of (a, b) sample P300 and (c, d) sample T400

表S3 样品P300、T400的矩形选区分析和选点分析结果(原子分数)

Table S3 Area scanning and spot scanning results (Atomic percent) of samples P300 and T400

Sample P300 (Fig. S5(a))
Area	Co/%	Sb/%	Area	Co/%	Sb/%
Area a1	18.24	81.76	Area c1	20.11	79.89
Area a2	17.54	82.46	Area c2	18.77	81.23
Area a3	17.99	82.01	Area c3	20.91	79.09
Area a4	18.14	81.86	Area c4	19.12	80.88
Mean value	17.98	82.02	Mean value	19.73	80.27
Sample P300 (Fig. S5(b))			Sample T400 (Fig. S5(d))
Spot	Co/%	Sb/%	Spot	Co/%	Sb/%
Spot b1	15.69	84.31	Spot d1	19.87	80.13
Spot b2	19.65	80.35	Spot d2	19.19	80.81
Spot b3	14.22	85.78	Spot d3	19.76	80.24
Spot b4	17.23	82.77	Spot d4	19.82	80.18
Spot b5	18.87	81.13	Spot d5	21.77	78.23
Spot b6	21.34	78.66	Spot d6	22.09	77.91
Spot b7	18.58	81.42	Spot d7	21.68	78.32
Spot b8	16.64	83.36	Spot d8	18.56	81.44
Spot b9	20.75	79.25	Spot d9	18.58	81.42
Mean value	18.11	81.89	Mean value	20.15	79.85

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激光诱导方钴矿自蔓延高温合成过程研究

Laser-induced Self-propagating High-temperature Synthesis of Skutterudite

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