高压调控锰酸盐晶体磁热效应的研究进展

doi:10.16553/j.cnki.issn1000-985x.2024.0324

摘要/Abstract

摘要： 在凝聚态物理领域，随着高压实验技术不断取得进步，探究材料在高温、高压、强磁场等环境下的物理性质已成为切实可行且行之有效的研究路径。锰酸盐的晶体结构和物理化学性质相对稳定，具有成本较为低廉的优势，通过调节居里温度可以使锰酸盐在室温附近表现出合适的磁热性能。本文概述了近年来极端条件下不同带宽类型掺杂锰酸盐材料磁热效应的研究进展，重点强调了压力在调控磁性材料的磁有序强度和温度、相变特征及磁热性能等方面的特殊作用。

关键词: 掺杂锰酸盐; 高温高压; 调控; 新型磁制冷材料; 相变特征; 磁热效应

Abstract: In the field of condensed matter physics， with the continuous progress of high pressure experimental technique， it has become a practical and effective research path to investigate the physical properties of materials under extreme conditions such as high temperature， high pressure and strong magnetic field. The crystal structure and physicochemical properties of manganates are relatively stable， and they have the advantage of lower cost. By adjusting the Curie temperature， manganates can exhibit suitable magnetocaloric effects near room temperature. This paper summarizes the researches of magnetocaloric effect of various bandwidth types of doped manganate materials under extreme conditions in recent years， where the role of pressure is emphasized in regulating the intensity and temperature of magnetic ordering state， the nature of magnetic phase transitions and the magnetocaloric properties of magnetic materials.

Key words: manganate doping; high temperature and high pressure; modulation; novel magnetic cooling material; phase transition characterization; magnetocaloric effect

中图分类号:

O469

朱雨革, 程栩逸, 高湉. 高压调控锰酸盐晶体磁热效应的研究进展[J]. 人工晶体学报, 2025, 54(8): 1379-1387.

ZHU Yuge, CHENG Xuyi, GAO Tian. Research Progress on Modulating the Magnetocaloric Effect of Manganate Crystals under High Pressure[J]. Journal of Synthetic Crystals, 2025, 54(8): 1379-1387.

图/表 6

图1 立方ABO3结构示意图［22］

Fig.1 Schematic diagram of cubic ABO3 structure［22］

图2 在常压（a）和6 GPa（b）高压下合成的La0.75Sr0.25Mn0.9Co0.1O3在0~7 T磁场下的等温磁熵变化［30］

Fig.2 Isothermal magnetic entropy changes of La0.75Sr0.25Mn0.9Co0.1O3 synthesized at atmospheric pressure （a） and high pressure of 6 GPa （b） under 0~7 T magnetic field［30］

图3 La0.35Pr0.35Ca0.3MnO3最大磁熵变随磁场（a）和压力（b）的变化［33］

Fig.3 Variation of maximum magnetic entropy change with magnetic field （a） and pressure （b） for La0.35Pr0.35Ca0.3MnO3［33］

图4 La0.35Pr0.35Ca0.3MnO3样品RCP随磁场（a）和压力（b）的变化［33］

Fig.4 Variation of RCP with magnetic field （a） and pressure （b） for La0.35Pr0.35Ca0.3MnO3 samples［33］

图5 La1-x Na x MnO3 （x=0.05和0.1）在不同磁场下的熵变。（a），（b）环境压力；（c），（d）1.1 GPa压力，插图为不同磁场下的相对制冷能力［38］

Fig.5 Entropy change of La1-x Na x MnO3 （x=0.05 and 0.1） at different magnetic fields. （a），（b） At ambient pressure；（c），（d） at 1.1 GPa pressure， the inset shows relative cooling capacity under different magnetic fields［38］

表1 压力下的掺杂锰酸盐晶体的最大磁熵变和相对制冷能力

Table 1 Maximum magnetic entropy change and relative cooling capacity of doped manganate crystals under pressure

Composition	T_C/K	Δµ₀H/T	P/GPa	-ΔS_m^max/（J·kg^-1·K^-1）	RCP/（J·kg^-1）	Morphology	Reference
La_0.8Sr_0.2MnO₃	302	5	0.677	~5.75	—	Single	［26］
La_0.4Bi_0.3Sr_0.3MnO₃	240	5	0.91	3.1	—	Polycrystalline	［27］
La_0.75Sr_0.25Mn_0.9Co_0.1O₃	243	7	4	3.75	404.78	Polycrystalline	［28］
La_0.75Sr_0.25MnO₃	325	7	6	5.21	364.52	Polycrystalline	［29］
La_0.75Sr_0.25Mn_0.9Co_0.1O₃	270	7	6	4.23	384.62
La_0.75Sr_0.25Mn_0.9Co_0.2O₃	211	7	6	3.53	384.66
La_0.75Sr_0.25Mn_0.9Co_0.1O₃	292	7	0	4.96	365.50	Polycrystalline	［30］
La_0.75Sr_0.25Mn_0.9Co_0.1O₃	274	7	6	3.95	403.92	Polycrystalline	［30］
La_0.69Ca_0.31MnO₃	213.5	5	0	8.5	—	Single	［31］
La_0.69Ca_0.31MnO₃	236.5	5	1.1	~8.4	—	Single	［31］
La_0.7Ca_0.3MnO₃	268.5	5	1.1	~7.7	—	Single	［32］
La_0.35Pr_0.35Ca_0.3MnO₃	167	5	0.91	7.26	310	Polycrystalline	［33］
Pr_0.6Ca_0.4Mn_0.96Co_0.04O₃	105.6	5	0.91	~5.5	~305	Polycrystalline	［34］
Pr_0.6Ca_0.4Mn_0.96Cr_0.04O₃	133	5	0.95	~5.1	~308	Polycrystalline	［34］
（Sm_0.8Nd_0.2）_0.52Sr_0.48MnO₃	136	5	1.17	~5.9	~145	Single	［37］
La_0.95Na_0.05MnO₃	249.7	3	1.1	5.66	~148	Polycrystalline	［38］
La_0.9Na_0.1MnO₃	269.6	3	1.1	5.12	106.9	Polycrystalline	［38］
La_0.7K_0.2Mn_1.1O₃	287	1	1.4	1.44	37	Polycrystalline	［39］
La_0.8Na_0.2MnO₃	320	1	0.8	0.92	40.8	Polycrystalline	［40］
La_0.75Cd_0.05Na_0.2MnO₃	316	1	0.8	0.93	44.3	Polycrystalline	［40］

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