CaZrO<sub>3</sub>改性(Na, K)NbO<sub>3</sub>基无铅陶瓷电学性能的温度稳定性

陈小明; 王明焱; 唐木智明; 李国荣

doi:10.7498/aps.70.20210440

摘要

压电陶瓷广泛用于驱动器、传感器等电子领域, 但是目前主要使用的压电陶瓷是铅基陶瓷. 基于保护环境和社会可持续发展的需要, 无铅压电陶瓷的研发变得迫切. 无铅压电陶瓷(K,Na)NbO₃(KNN)因具有较高压电常数和居里温度, 而受到广泛关注. 然而较差的温度稳定性限制了其应用. 本文通过二步合成法制备了电学性能温度稳定的(1–x)(Na_0.52K_0.48)_0.95Li_0.05NbO₃-xCaZrO₃(NKLN-xCZ)陶瓷, 研究了CaZrO₃对KNN基陶瓷微结构及电学性能的作用. 研究结果表明: 适量CaZrO₃改善了样品烧结性能, 得到了致密陶瓷. 随CaZrO₃增加, NKLN-CZ陶瓷的三方相(R)-四方相(T)共存出现在组分为 $0.05\leqslant x \leqslant 0.06.$ x = 0.05时, 陶瓷样品不但具有高居里温度(T_c= 373 ℃), 而且表现出良好电学性能(d₃₃= 198 pC/N, k_p= 39%, ε_r= 1140, tanδ =0.034, P_r= 21 μC/cm², E_c= 18.2 kV/cm). 此外, 该陶瓷由于存在弥散R-T相变, 导致其相变温度区间拓宽, 因此, 该陶瓷具有较好的电学性能温度稳定: 在温度范围为–50—150 ℃, NKLN–0.05CZ陶瓷的k_p保持在34%—39% (k_p变化量 $\leqslant13\%$).

关键词:

Abstract

Piezoelectric ceramics are mainly used in the electronic fields such as actuators, sensors, etc. However, at present the piezoelectric ceramics widely used are lead-based ceramics, which are detrimental to the environment. Based on the needs of environmental protection and social sustainable development, the research of lead-free piezoelectric ceramics becomes urgent. (K, Na) NbO₃ (KNN) lead-free piezoelectric ceramics have attracted much attention due to their high piezoelectric coefficient and Curie temperature. However, temperature stability of ceramics is poor, which limits their applications. In this work, (1–x)(Na_0.52K_0.48)_0.95Li_0.05NbO₃-xCaZrO₃(NKLN-xCZ) ceramics with temperature stability are prepared by two-step synthesis. The effects of CaZrO₃ on the phase structure, microstructure and electrical properties of KNN-based ceramics are studied. The results show that the appropriate introduction of CaZrO₃ can improve the sintering properties of the samples and obtain dense ceramics. All the samples have typical perovskite structure without impurity. With the increase of CaZrO₃, the temperature of orthorhombic(O)-Tetragonal (T) phase transition (T_O-T) and Curie temperature (T_C) move from high temperature to low temperature, while the transition temperature (T_O-R) moves from low temperature to room temperature, and then, tetragonal (T) phase and rhombohedral (R) phase coexist in NKLN-xCZ ceramics as $0.05 \leqslant x \leqslant0.06 $. When x = 0.05, the ceramics have high Curie temperature (T_c = 373 ℃), and show good piezoelectric and ferroelectric properties (piezoelectric constant d₃₃ = 198 pC/N, planar electromechanical coupling coefficient k_p = 39%, ε_r = 1140, tanδ = 0.034, P_r = 21 μC/cm², E_c = 18.2 kV/cm) because of the density of ceramics and existence of R-T phase boundary around room temperature. In addition, the relative permittivity of ceramics changes with the increase of frequency, which shows a certain relaxation behavior. The relaxation characteristics can be expressed by the modified Curie-Weiss law (1/ε_r–1/ε_r,m) = C(T–T_m)^α. With the increase of CZ content, the dispersion coefficient α of ceramics increases (x = 0.07, α = 1.96), which can be ascribed to A-site cation disorder induced by the addition of CZ. The temperature range of phase transition is widened because of the diffused R-T phase transition. Therefore, the ceramics have temperature-stable electrical properties: the k_p of NKLN-0.05CZ ceramics is kept at 34%–39% (variation of k_p $\leqslant 13\% $) in a temperature range of –50–150 ℃. It provides methods and ideas for further exploring the temperature stability of KNN-based ceramics.

Keywords:

作者及机构信息

1.
贵州理工学院, 贵州省轻金属材料制备技术重点实验室, 贵阳　550003

2.
贵州理工学院材料与能源工程学院, 贵阳　550003

3.
中国科学院上海硅酸盐研究所, 上海　200050

4.
成都市消防救援支队, 成都　610000

5.
日本富山县立大学工学部, 富山　9390398

通信作者: 陈小明, chen-xm123@163.com

基金项目: 国家自然科学基金地区科学基金(批准号: 52162015)、贵州省科学技术基金项目(批准号: [2020]1Y204)、贵州省教育厅基金项目(批准号: KY[2018]253)和贵州理工学院博士启动基金(批准号: XJGC20190920)资助的课题

Authors and contacts

1.
Key Laboratory of Light Metal Materials Processing Technology of Guizhou Province, Guizhou Institute of Technology, Guiyang 550003, China

2.
School of Materials and Energy Engineering, Guizhou Institute of Technology, Guiyang 550003, China

3.
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

4.
Fire and Rescue Branch of Chengdu city, Chengdu 610000, China

5.
Faculty of Engineering, Toyama Prefectural University, Toyama 9390389, Japan

Corresponding author: Chen Xiao-Ming, chen-xm123@163.com

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 52162015), the Science and Technology Fund of Education Bureau of Guizhou Province, China (Grant No. [2020]1Y204), the Natural Science Foundation of Department of Education of Guizhou Province, China (Grant No. KY [2018]253), and the Doctor Starting Foundation of Guizhou Institute of Technology, China (Grant No. XJGC20190920)

文章全文 : translate this paragraph

参考文献

[1]	Uchinoin K 1997 Piezoelectric Actuators and Ultrasonic Motors (Boston: Springer US) pp265−273
[2]	Jaffe B, Cook W R, Jaffe H 1971 Piezoelectric ceramics (New York: Academic Press) pp1−5
[3]	Guo R, Cross L E, Park S E, Noheda B, Cox D E, Shirane G 2000 Phys. Rev. Lett. 84 5423 Google Scholar
[4]	Wang K, Shen Z Y, Zhang B P, Li J F 2014 J. Inorg. Mater. 29 13 Google Scholar
[5]	Xiao D Q, Wu J G, Wu L, Zhu J G, Yu P, Lin D M, Liao Y W, Sun Y 2009 J. Mater. Sci. 44 5408 Google Scholar
[6]	Zhang S, Xia R, Shrout T R 2007 J. Electroceram. 19 251 Google Scholar
[7]	Rödel J, Jo W, Seifert K T, Anton E M, Granzow T, Damjanovic D 2009 J. Am. Ceram. Soc. 92 1153 Google Scholar
[8]	Saito Y, Takao H, Tani T, Nonoyama T, Takatori K, Homma T, Nagaya T, Nakamura M 2004 Nature 432 84 Google Scholar
[9]	Chen K, Xu G, Yang D, Wang X, Li J 2007 J. Appl. Phys. 101 044103 Google Scholar
[10]	陈超, 江向平, 卫巍, 李小红, 魏红斌, 宋福生 2011 60 107704 Google Scholar Chen C, Jiang X P, Wei W, Li X H, Wei H B, Song F S 2011 Acta Phys. Sin 60 107704 Google Scholar
[11]	Liang W, Wu W, Xiao D, Zhu J 2011 J. Am. Ceram. Soc. 94 4317 Google Scholar
[12]	Zhang Y, Li L Y, Bai W F, Shen B, Zhai J W, Li B 2015 Rsc Adv. 5 19647 Google Scholar
[13]	Zheng T, Wu J, Xiao D, Zhu J, Wang X, Xin L, Lou X 2015 ACS Appl. Mater. Interfaces 7 5927 Google Scholar
[14]	Zhang Y, Shen B, Zhai J W, Zeng H R 2016 J. Am. Ceram. Soc. 99 752 Google Scholar
[15]	邢洁, 谭智, 郑婷, 吴家刚, 肖定全, 朱建国 2020 69 127707 Google Scholar Xing J, Tan Z, Zheng T, Wu J G, Zhu J G 2020 Acta Phys. Sin. 69 127707 Google Scholar
[16]	Zhang S J, Xia R, Shrout T R 2007 Appl. Phys. Lett. 91 132913 Google Scholar
[17]	Yao F Z, Wang K, Jo W, Webber K G, Comyn T P, Ding J X, Xu B, Cheng L Q, Zheng M P, Hou Y D, Li J F 2016 Adv. Funct. Mater. 26 1217 Google Scholar
[18]	Zhang M H, Wang K, Du Y J, Dai G, Sun W, Li G, Hu D, Thong H C, Zhao C, Xi X Q, Yue Z X, Li J F 2017 J. Am. Chem. Soc. 139 3889 Google Scholar
[19]	Tao H, Wu H, Liu Y, Zhang Y, Wu J, Li F, Lyu X, Zhao C, Xiao D, Zhu J, Pennycook S J 2019 J. Am. Chem. Soc. 141 13987 Google Scholar
[20]	Onoe M, Jumonji H 1967 J. Acoust. Soc. Am. 41 974 Google Scholar
[21]	Liang W, Wu W, Xiao D, Zhu J, Wu J 2011 J. Mater. Sci. 46 6871 Google Scholar
[22]	Zhang B, Wu J, Wang X, Cheng X, Zhu J, Xiao D 2013 Curr. Appl Phys. 13 1647 Google Scholar
[23]	Zuo R, Fang X, Ye C, Li L 2007 J. Am. Ceram. Soc. 90 2424 Google Scholar
[24]	Chen X, Zeng J, Kim D, Zheng L, Lou Q, Hong Park C, Li G 2019 Mater. Chem. Phys. 231 173 Google Scholar
[25]	Chen X, Ruan X, Zhao K, He X, Zeng J, Li Y, Zheng L, Park C H, Li G 2015 J. Alloys Compd. 632 103 Google Scholar
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[27]	Uchino K, Nomura S 1982 Ferroelectrics 44 55

施引文献

图 1 NKLN-xCZ陶瓷的表面形貌　(a) x = 0; (b) x = 0.04; (c) x = 0.05; (d) x = 0.09

Fig. 1. SEM surface micrographs of NKLN-xCZ ceramics: (a) x = 0; (b) x = 0.04; (c) x = 0.05; (d) x = 0.09.

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图 2 NKLN-xCZ陶瓷密度

Fig. 2. Density of the NKLN-xCZ ceramics.

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图 3 (a) NKLN-xCZ陶瓷晶相结构; (b) NKLN-xCZ陶瓷在40°−50°特征峰

Fig. 3. (a) X-ray diffraction patterns of NKLN-xCZ ceramics; (b) the magnification for NKLN-CZ ceramics in the range of 40°−50°.

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图 4 在–100到200 ℃温度范围内NKLN-xCZ陶瓷的介温曲线(1 kHz)

Fig. 4. Temperature dependence of dielectric constant and dielectric loss for NKLN-.CZ ceramics measured at 1 kHz in the temperature range from –100 to 200 ℃.

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图 5 (a)−(c)在30到500 ℃温度范围内NKLN-xCZ陶瓷介温曲线; (d) NKLN-xCZ陶瓷ln(1/ε_r–1/ε_m)与ln(T–T_m)关系曲线

Fig. 5. (a)−(c) Temperature dependence of dielectric constant for NKLN-xCZ ceramics in the temperature range from 30 to 500 ℃; (d) plots of ln(1/ε_r–1/ε_m) as a function of ln(T–T_m) for the NKLN-xCZ ceramics.

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图 6 NKLN-xCZ陶瓷的相图

Fig. 6. Phase diagram of NKLN-xCZ ceramics.

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图 7 NKLN-xCZ陶瓷的铁电性能

Fig. 7. Ferroelectric properties of NKLN-xCZ ceramics

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图 8 NKLN-xCZ陶瓷的压电与介电性能

Fig. 8. piezoelectric and dielectric properties of NKLN-xCZ ceramics.

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图 9 (a)NKLN-0.05 CZ陶瓷性能温度稳定性; (b)−(f) NKLN–0.05 CZ陶瓷谐振-反谐振图谱(T = –50, 25, 50, 100, 150 ℃)

Fig. 9. (a) The temperature-stable electrical properties of NKLN-0.05 CZ ceramics; (b)−(f) impedance as a function of frequency of NKLN-0.05 CZ ceramics (T = –50, 25, 50, 100, 150 ℃).

下载: 全尺寸图片幻灯片

map

[1]	Uchinoin K 1997 Piezoelectric Actuators and Ultrasonic Motors (Boston: Springer US) pp265−273
[2]	Jaffe B, Cook W R, Jaffe H 1971 Piezoelectric ceramics (New York: Academic Press) pp1−5
[3]	Guo R, Cross L E, Park S E, Noheda B, Cox D E, Shirane G 2000 Phys. Rev. Lett. 84 5423 Google Scholar
[4]	Wang K, Shen Z Y, Zhang B P, Li J F 2014 J. Inorg. Mater. 29 13 Google Scholar
[5]	Xiao D Q, Wu J G, Wu L, Zhu J G, Yu P, Lin D M, Liao Y W, Sun Y 2009 J. Mater. Sci. 44 5408 Google Scholar
[6]	Zhang S, Xia R, Shrout T R 2007 J. Electroceram. 19 251 Google Scholar
[7]	Rödel J, Jo W, Seifert K T, Anton E M, Granzow T, Damjanovic D 2009 J. Am. Ceram. Soc. 92 1153 Google Scholar
[8]	Saito Y, Takao H, Tani T, Nonoyama T, Takatori K, Homma T, Nagaya T, Nakamura M 2004 Nature 432 84 Google Scholar
[9]	Chen K, Xu G, Yang D, Wang X, Li J 2007 J. Appl. Phys. 101 044103 Google Scholar
[10]	陈超, 江向平, 卫巍, 李小红, 魏红斌, 宋福生 2011 60 107704 Google Scholar Chen C, Jiang X P, Wei W, Li X H, Wei H B, Song F S 2011 Acta Phys. Sin 60 107704 Google Scholar
[11]	Liang W, Wu W, Xiao D, Zhu J 2011 J. Am. Ceram. Soc. 94 4317 Google Scholar
[12]	Zhang Y, Li L Y, Bai W F, Shen B, Zhai J W, Li B 2015 Rsc Adv. 5 19647 Google Scholar
[13]	Zheng T, Wu J, Xiao D, Zhu J, Wang X, Xin L, Lou X 2015 ACS Appl. Mater. Interfaces 7 5927 Google Scholar
[14]	Zhang Y, Shen B, Zhai J W, Zeng H R 2016 J. Am. Ceram. Soc. 99 752 Google Scholar
[15]	邢洁, 谭智, 郑婷, 吴家刚, 肖定全, 朱建国 2020 69 127707 Google Scholar Xing J, Tan Z, Zheng T, Wu J G, Zhu J G 2020 Acta Phys. Sin. 69 127707 Google Scholar
[16]	Zhang S J, Xia R, Shrout T R 2007 Appl. Phys. Lett. 91 132913 Google Scholar
[17]	Yao F Z, Wang K, Jo W, Webber K G, Comyn T P, Ding J X, Xu B, Cheng L Q, Zheng M P, Hou Y D, Li J F 2016 Adv. Funct. Mater. 26 1217 Google Scholar
[18]	Zhang M H, Wang K, Du Y J, Dai G, Sun W, Li G, Hu D, Thong H C, Zhao C, Xi X Q, Yue Z X, Li J F 2017 J. Am. Chem. Soc. 139 3889 Google Scholar
[19]	Tao H, Wu H, Liu Y, Zhang Y, Wu J, Li F, Lyu X, Zhao C, Xiao D, Zhu J, Pennycook S J 2019 J. Am. Chem. Soc. 141 13987 Google Scholar
[20]	Onoe M, Jumonji H 1967 J. Acoust. Soc. Am. 41 974 Google Scholar
[21]	Liang W, Wu W, Xiao D, Zhu J, Wu J 2011 J. Mater. Sci. 46 6871 Google Scholar
[22]	Zhang B, Wu J, Wang X, Cheng X, Zhu J, Xiao D 2013 Curr. Appl Phys. 13 1647 Google Scholar
[23]	Zuo R, Fang X, Ye C, Li L 2007 J. Am. Ceram. Soc. 90 2424 Google Scholar
[24]	Chen X, Zeng J, Kim D, Zheng L, Lou Q, Hong Park C, Li G 2019 Mater. Chem. Phys. 231 173 Google Scholar
[25]	Chen X, Ruan X, Zhao K, He X, Zeng J, Li Y, Zheng L, Park C H, Li G 2015 J. Alloys Compd. 632 103 Google Scholar
[26]	Zhao P, Zhang B P, Li J F 2007 Appl. Phys. Lett. 90 242909 Google Scholar
[27]	Uchino K, Nomura S 1982 Ferroelectrics 44 55

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CaZrO₃改性(Na, K)NbO₃基无铅陶瓷电学性能的温度稳定性