Ba0.57Sr0.39Ca0.03Ti1.01NbxO3基正温度系数陶瓷材料制备及电学性能研究

doi:10.15541/jim20250446

摘要/Abstract

摘要： 低居里温度钛酸钡基正温度系数(Positive temperature coefficient, PTC)陶瓷因具有低温环境下电阻率随温度急剧变化的特性,能够满足精密测温传感组件在低温领域的使用需求,在深空探测等领域具有广泛的应用前景。但是,低居里温度钛酸钡基PTC材料难以兼具小的低温电阻率与高的升阻比。本研究旨在通过元素掺杂优化低居里温度钛酸钡基PTC陶瓷的性能,解决低温电阻率偏高与升阻比不足的矛盾。采用固相合成法制备了Ba_0.57Sr_0.39Ca_0.03Ti_1.01Nb_xO₃低居里温度钛酸钡基PTC热敏陶瓷材料。通过X射线分析衍射(XRD)分析,扫描电子显微镜(SEM)分析和电性能测试研究了陶瓷结构与性能的关系。不同烧结温度样品的电性能测试证明1375 ℃是最优烧结温度,X射线衍射分析确定了样品具有单一晶相,扫描电子显微镜分析证实了Nb对晶粒的细化作用。对不同Nb掺杂含量的样品进行电阻率-温度测试,发现在x = 0.0025、0.0030时,材料的低温电阻率下降至10³ Ω·cm,升阻比达到6,具有优良的PTC效应。介电常数-温度谱测试进一步确定了材料的居里温度为0 ℃,并发现介电常数随Nb掺杂含量的增加呈现波动式上升。交流复阻抗谱测试表明材料PTC效应的产生与晶界效应有关。通过掺入Sr使得材料的居里温度降低至0 ℃,使用Nb作为施主掺杂元素降低了材料低温电阻率,向材料体系中引入Mn提高了材料的升阻比。该研究成功制备了居里温度低、低温电阻率小且升阻比高的钛酸钡基PTC陶瓷,为航天领域的低温高精度温度传感组件研发提供了新思路。

关键词: 钛酸钡, 低居里温度, PTC热敏陶瓷

Abstract: Low Curie temperature Barium titanate-based positive temperature coefficient (PTC) ceramics, which exhibit significant resistivity changes with temperature in low temperature environments, fulfill the demand for precise temperature sensor components and hold broad application potential in deep space exploration. However, achieving both low low-temperature resistivity and high PTC intensity remains challenging in low Curie temperature barium titanate-based PTC materials. This study focuses on optimizing the performance of low-Curie-temperature barium titanate-based PTC ceramics through element doping, addressing the critical contradiction between elevated low-temperature resistivity and insufficient PTC intensity. A low Curie temperature barium titanate-based PTC thermistor ceramic material Ba_0.57Sr_0.39Ca_0.03Ti_1.01Nb_xO₃ was prepared via solid-state synthesis. X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and electric tests were implemented to clarify the mechanism of structures and properties. Electrical property tests on samples sintered at different temperatures confirmed 1375 ℃ as the optimal sintering temperature. XRD analysis verified single crystalline phase composition. SEM images confirmed niobium’s role in grain refinement. Resistivity-temperature tests on samples with varying Nb doping content showed that at x = 0.0025 and 0.0030, the low-temperature resistivity dropped to 10³ Ω·cm with a PTC intensity of 6, demonstrating excellent PTC characteristics. Dielectric constant-temperature spectra further confirmed the Curie temperature at 0 ℃ and the dielectric constant showed an oscillatory increase with the rise of Nb doping content. AC complex impedance spectra revealed that the PTC effect originates from grain boundary effects. Strontium doping reduced the Curie temperature to 0 ℃, while niobium as a donor dopant decreased the low-temperature resistivity. Manganese was introduced to enhance the PTC intensity. This study pioneered the fabrication of barium titanate-based PTC ceramics exhibiting low Curie temperatures, exceptionally small low-temperature resistivity, and high PTC intensity, establishing a paradigm shift for developing cryogenic temperature sensors critical to aerospace thermal management systems.

Key words: barium taitanate, low Curie temperature, PTC thermistor ceramics

中图分类号:

TQ174

周文昊, 欧阳琪, 马名生, 陆毅青, 刘志甫. Ba_0.57Sr_0.39Ca_0.03Ti_1.01Nb_xO₃基正温度系数陶瓷材料制备及电学性能研究[J]. 无机材料学报, DOI: 10.15541/jim20250446.

ZHOU Wenhao, OUYANG Qi, MA Mingsheng, LU Yiqing, LIU Zhifu. Synthesis and Electrical Characteristics of Ba_0.57Sr_0.39Ca_0.03Ti_1.01Nb_xO₃ Positive Temperature Coefficient Ceramics[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250446.

参考文献

[1] FENG J C, ZHANG X F, LIAO X,et al. Spacecraft intelligent autonomous thermal control method based on space environment prediction. Spacecraft Engineering, 2021, 30(05): 45.
[2] BECKER J A, GREEN C B, PEARSON G L.Properties and uses of thermistors-thermally sensitive resistors.Electrical Engineering, 1946, 65(11): 711.
[3] LI Y Y, LI G R, WANG T B,et al. Effects of niobium-doping on the structure and electrical properties of (Ba,Bi,Na)TiO₃-based PTCR ceramics. Journal of Inorganic Materials, 2009, 24(2): 374.
[4] AHN J H, LEEGHIM H, LEE C Y.Resistance characteristics and particle arrangement of smart paint for surface temperature sensor.Journal of Nanoscience and Nanotechnology, 2020, 20(7): 4263.
[5] ZHANG W, ZHAO R, CHENG W-L.Temperature control performance of a spaceborne PTC heating system: dynamic modeling and parametric analysis.Thermal Science and Engineering Progress, 2023, 44: 102062.
[6] BAKHTIAR S U H, DONG T, XUE B,et al. Positive temperature coefficient materials for intelligent overload protection in the new energy era. Materials Today, 2023, 71: 108.
[7] YU A, LI Q, FAN D,et al. Study on positive temperature coefficient of resistivity of co-doped BaTiO₃ with Curie temperature in room temperature region. Science China Technological Sciences, 2019, 62(5): 811.
[8] YU A, LI Q.Temperature-dependent resistivity performance of Mn/Y-doped Ba₁-_xSr_xTiO₃ compositions with potential thermal control applications. Ceramics International, 2020, 46(7): 8796.
[9] SANG Z K, ZHAO R, CHENG W L.Study on temperature control characteristics of low-resistivity ceramic-based PTC material.Journal of Beijing University of Aeronautics and Astronautics, 2023, 49(08): 2147.
[10] ZHOU Y X, YANG D, JIANG G M,et al. Effect of Y₂O₃ doping on dielectric-temperature and resistivity-temperature characteristics of barium strontium titanate ceramics. High Voltage Engineering, 2023, 49(11): 4686.
[11] WANG Y, CHEN X.Investigation of the positive temperature coefficient resistivity of Nb-doped Ba_0.55Sr_0.45TiO₃ ceramics.Crystals, 2024, 14(5): 419.
[12] XU W, WANG W, ZHANG X, et al.(Ba_0.55Sr_0.45)₁-_xLa_xTi_1.01O₃-Bi_0.5Na_0.5TiO₃ positive temperature coefficient resistivity ceramics with low Curie temperature, 2024, 17(8): 1812.
[13] PU Y, WU H, WEI J,et al. Influence of doping Nb⁵+ and Mn²+ on the PTCR effects of Ba_0.92Ca_0.05(Bi_0.5Na_0.5)_0.03TiO₃ ceramics. Journal of Materials Science: Materials in Electronics, 2011, 22(9): 1479.
[14] LENG S L, JIA F H, ZHONG Z K,et al. Fabrication of high T_C BaTiO₃-(Bi_0.5Na_0.5)TiO₃ lead-free positive temperature coefficient of resistivity ceramics. Journal of Inorganic Materials, 2015, 30(6): 576.
[15] CHENG X, CHEN X, LI X,et al. Influence of Ba/Ti ratio on PTCR effect of Ba_m(Ti₁-_xNb_x)O₃ ceramics prepared by the reduction sintering-reoxidation method. Modern Physics Letters B, 2018, 32(34n36): 1840071.
[16] LIU Y S.The preparation and applications of the PTC thermistor heater.Piezoelectrics & Acoustooptics, 1981(4): 45.
[17] MORRISON F D, COATS A M, SINCLAIR D C, et al. Charge compensation mechanisms in La-doped BaTiO₃. Journal of Electroceramics, 2001, 6(3): 219.
[18] LENG S, CHENG H, ZHANG R,et al. Electrical properties of La-Mn-codoped BaTiO₃-(Bi_0.5Na_0.5)TiO₃ lead-free PTCR ceramics. Ceramics International, 2021, 47(21): 30963.
[19] BELL J G, GRAULE T, STUER M.Barium titanate-based thermistors: Past achievements, state of the art, and future perspectives.Applied Physics Reviews, 2021, 8(3): 031318.
[20] SETTER N, CROSS L E.The role of B-site cation disorder in diffuse phase transition behavior of perovskite ferroelectrics.Journal of Applied Physics, 1980, 51(8): 4356.
[21] HENNINGS D.Barium titanate based ceramic materials for dielectric use.International Journal of High Technology Ceramics, 1987, 3(2): 91.
[22] LI Y L, QU Y F.Substitution preference and dielectric properties of Y³+-doped Ba_0.62Sr_0.38TiO₃ ceramics.Materials Chemistry and Physics, 2008, 110(1): 155.
[23] ZHAO R Y, OUYANG Q, MA M S,et al. Influence of content of Bi_0.5Na_0.5TiO₃ and Bi_0.5K_0.5TiO₃ on the properties of lead-free PTC ceramics of the ternary solid solution system. Materials Reports, 2023, 37(10): 114.
[24] TANG X F, TANG Z L, ZHOU Z G.Complex impedance spectra of BaTiO₃ based PTCR ceramics.Journal of Inorganic Materials, 2000, 15(6): 1037.
[25] LIU J, JIN G, CHEN Y,et al. Properties of yttrium-doped barium titanate ceramics with positive temperature coefficient of resistivity and a novel method to evaluate the depletion layer width. Ceramics International, 2019, 45(5): 6119.
[26] HAO S E,WEI Y D.Effects of Sm₂O₃ doping on structure and electric characteristics of BaTiO₃ ceramics.Journal of Inorganic Materials, 2003(05): 1069.

Ba_0.57Sr_0.39Ca_0.03Ti_1.01Nb_xO₃基正温度系数陶瓷材料制备及电学性能研究

Synthesis and Electrical Characteristics of Ba_0.57Sr_0.39Ca_0.03Ti_1.01Nb_xO₃ Positive Temperature Coefficient Ceramics

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