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

doi:10.15541/jim20220714

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 13

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

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

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 ℃

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

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 ℃

Fig. S1 Schematic diagram of the SHS device

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

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

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

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

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)

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

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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