钛酸铅系电子陶瓷的制备及其电性能
摘要
钛酸铅是一种典型的铁电材料，因为它居里点高、介电常数小、机电各向异性大，很适合应用于高温高频领域。但由于其四方矫顽场大，成为陶瓷的晶界能高，使它在退火过程中经过居里点时，容易产生微裂纹，而使其应用受限。为了解决这一问题，科研工作者进行了各种各样的探索：(1)对液相合成方法的研究，目的在于获得结晶良好的粉体原料，以降低内应力；(2)采用固相法合成粉体原料，掺杂后研究其物理性能。所以我们选择钛酸铅系电子陶瓷粉体的水热合成和陶瓷的电学性质作为本论文的研究内容。与其他方法相比，水热法不需要高温煅烧，在533K或更低的温度下就可获得各种陶瓷材料，就钛酸铅而言，这么低的温度不仅可以降低在煅烧和球磨过程中杂质的引入，还可以减少铅的挥发。
本论文的主要内容如下：
一、文献综述
总结了钛酸铅系电子陶瓷及粉体的制备方法，比较了各种方法的优缺点；叙述了电子陶瓷的电性能如：压电性、热释电性和铁电性，探讨了铁电性产生的机理；简单介绍了钛酸铅系电子陶瓷的应用。
二、纯钛酸铅电子陶瓷的制备及其电性能研究
采用水热法制备了纯钛酸铅纳米晶，考察了多种水热条件：反应物浓度、水热温度和时间、介质碱度和铅钛比等对钛酸铅粉体微观形貌和晶体结构的影响，分析了这些水热条件的影响机理，找到了较好的纯钛酸铅的水热合成条件。目前我们基本上可以通过控制水热条件得到不同粒径的钛酸铅粉体，为今后研究钛酸铅陶瓷的晶粒尺寸效应奠定了基础。
采用传统方法制得了纯钛酸铅陶瓷，考察了多种影响因素：压片压力、烧结温度、烧结时间和烧结氛围等对钛酸铅陶瓷微观形貌和晶体结构的影响，找到了较为适宜的制陶条件。
测量了室温下纯钛酸铅陶瓷的介电频谱。
三、掺杂钛酸铅陶瓷的制备及其电性能研究
在由纯钛酸铅确定的较佳的水热条件下，合成了一系列掺杂钛酸铅粉体，掺杂方式包括A位和B位。其中A位包括等价掺杂和施主掺杂，等
价掺杂采用碱土金属(饭、sr、Ba:施主掺杂采用稀土金属La、Sm。B位
采用Zr。并且考察了这些元素的掺入量对钦酸铅粉体微观形貌和晶体结
构的影响，我们发现杂质元素的掺入会引起钦酸铅粉体粒径和四方性的改
变，元素不同影响不同。在由纯钦酸铅确定的较为适宜的制陶条件下，分
别制得了上述元素掺杂钦酸铅陶瓷，讨论了它们的掺入量对钦酸铅陶瓷微
观形貌和晶体结构的影响。
最后分别测量了室温下掺杂钦酸铅陶瓷的介电频谱，实验表明悯、衫、
钙、银、钡、错的掺入对钦酸铅陶瓷的介电常数和介电损耗均有不同程度
的影响。
Compared with other ferroelectronic materials, lead titanate (PbTi03) has many useful properties, including a high transition temperature (-763K), a low ratio for the planar-to-thickness coupling factor, a low aging rate of the dielectric constant, and low dielectric constant. Therefore, PbTi03 shows great promise as a stable pyroelectric and piezoeletric materials for high-temperature or high-frequency applications.
The advantage of hydrothermal processing is that many crystalline ceramic materials may be synthesized without a calcination step at temperature of 533K and lower. In the case of PbTi03, such low processing temperature eliminate volatilization, in addition to minimizing impurities associated with calcination and ball-milling steps.
The main points:
I . Review
In this part we have not only summarized the preparation methods of Lead-based titanate powders and ceramics, but also discussed the properties and application of the ceramics.
II. Preparation and electric properties of lead titanate ceramics
1. PbTi03 powders have been synthesized by suspending Ti(OC4H9)4 in aqueous solution of NaOH and Pb(COOCH3)2 3H20 at temperature ranging from 473K to 533K. Experiments show that the growth and morphology of hydrothermally derived lead titanate powders will depend strongly on the feedstock concentration, reaction time and temperature, NaOH concentration, and [Pb]/[Ti] ratio.
2. PbTi03 ceramics were prepared by conventional sintering method. The effect of sinter time, temperature and atmosphere on their growth and morphology has been examined.
3. The dielectric spectrum of PbTi03 ceramics has been carried out using HP4194A.
III. Preparation and electric properties of modified lead titanate ceramics
1. We have obtained La, Sm, Ca, Sr, Ba, and Zr-doped lead titanate powders and ceramics under the same conditions as fine PbTiO3. The influence of dopants on the size and morphology of PbTiO3 powders and ceramics has been investigated.
2. The dielectric spectra of modified PbTiO3 ceramics have been measured by HP4194A. The results indicate that the dopants will change the dielectric constant and tg 8 of PbTiO3.
本论文的主要内容如下：
一、文献综述
总结了钛酸铅系电子陶瓷及粉体的制备方法，比较了各种方法的优缺点；叙述了电子陶瓷的电性能如：压电性、热释电性和铁电性，探讨了铁电性产生的机理；简单介绍了钛酸铅系电子陶瓷的应用。
二、纯钛酸铅电子陶瓷的制备及其电性能研究
采用水热法制备了纯钛酸铅纳米晶，考察了多种水热条件：反应物浓度、水热温度和时间、介质碱度和铅钛比等对钛酸铅粉体微观形貌和晶体结构的影响，分析了这些水热条件的影响机理，找到了较好的纯钛酸铅的水热合成条件。目前我们基本上可以通过控制水热条件得到不同粒径的钛酸铅粉体，为今后研究钛酸铅陶瓷的晶粒尺寸效应奠定了基础。
采用传统方法制得了纯钛酸铅陶瓷，考察了多种影响因素：压片压力、烧结温度、烧结时间和烧结氛围等对钛酸铅陶瓷微观形貌和晶体结构的影响，找到了较为适宜的制陶条件。
测量了室温下纯钛酸铅陶瓷的介电频谱。
三、掺杂钛酸铅陶瓷的制备及其电性能研究
在由纯钛酸铅确定的较佳的水热条件下，合成了一系列掺杂钛酸铅粉体，掺杂方式包括A位和B位。其中A位包括等价掺杂和施主掺杂，等
价掺杂采用碱土金属(饭、sr、Ba:施主掺杂采用稀土金属La、Sm。B位
采用Zr。并且考察了这些元素的掺入量对钦酸铅粉体微观形貌和晶体结
构的影响，我们发现杂质元素的掺入会引起钦酸铅粉体粒径和四方性的改
变，元素不同影响不同。在由纯钦酸铅确定的较为适宜的制陶条件下，分
别制得了上述元素掺杂钦酸铅陶瓷，讨论了它们的掺入量对钦酸铅陶瓷微
观形貌和晶体结构的影响。
最后分别测量了室温下掺杂钦酸铅陶瓷的介电频谱，实验表明悯、衫、
钙、银、钡、错的掺入对钦酸铅陶瓷的介电常数和介电损耗均有不同程度
的影响。
Compared with other ferroelectronic materials, lead titanate (PbTi03) has many useful properties, including a high transition temperature (-763K), a low ratio for the planar-to-thickness coupling factor, a low aging rate of the dielectric constant, and low dielectric constant. Therefore, PbTi03 shows great promise as a stable pyroelectric and piezoeletric materials for high-temperature or high-frequency applications.
The advantage of hydrothermal processing is that many crystalline ceramic materials may be synthesized without a calcination step at temperature of 533K and lower. In the case of PbTi03, such low processing temperature eliminate volatilization, in addition to minimizing impurities associated with calcination and ball-milling steps.
The main points:
I . Review
In this part we have not only summarized the preparation methods of Lead-based titanate powders and ceramics, but also discussed the properties and application of the ceramics.
II. Preparation and electric properties of lead titanate ceramics
1. PbTi03 powders have been synthesized by suspending Ti(OC4H9)4 in aqueous solution of NaOH and Pb(COOCH3)2 3H20 at temperature ranging from 473K to 533K. Experiments show that the growth and morphology of hydrothermally derived lead titanate powders will depend strongly on the feedstock concentration, reaction time and temperature, NaOH concentration, and [Pb]/[Ti] ratio.
2. PbTi03 ceramics were prepared by conventional sintering method. The effect of sinter time, temperature and atmosphere on their growth and morphology has been examined.
3. The dielectric spectrum of PbTi03 ceramics has been carried out using HP4194A.
III. Preparation and electric properties of modified lead titanate ceramics
1. We have obtained La, Sm, Ca, Sr, Ba, and Zr-doped lead titanate powders and ceramics under the same conditions as fine PbTiO3. The influence of dopants on the size and morphology of PbTiO3 powders and ceramics has been investigated.
2. The dielectric spectra of modified PbTiO3 ceramics have been measured by HP4194A. The results indicate that the dopants will change the dielectric constant and tg 8 of PbTiO3.
引文
1．徐政，倪宏伟编著。现代功能陶瓷[M]。北京：国防工业出版社，1998．1～62
2. Tomonari Takeuchi, Mitsuharu Tabuchi, Isao Kondoh, Nobuyuki Tamari, and Hiroyuki Kageyama, "Synthesis of Dense Lead Titanate Ceramics with Submicrometer Grains by Spark Plasma Sintering," J. Am. Ceram. Soc[J]., 2000, 83 (3): 541-544. (1-4)
3. Ji-wei Zhai, Xi Yao, Ming-zhang Wu et al., "Preparation and microwave characterization of PbTiO_3 ceramic and powder," J. Phys. D: Appl. Phys.[J], 2001, (34): 1413～1416 (1-1)
4．江东亮等编。精细陶瓷材料[M]。中国物资出版社，2000．214
5．熊家林，贡长生，张可立主编，无机精细化学品的制备与应用[M]，化学工业出版社．1999．305～312
6. Jun-min Xue, Dong-mei Wan, John Wang et al., "Mechanochemical synthesis of nanosized lead titanate powders from oxides," Materials Letters. [J] , 1999, (39): 364～369 (1-7)
7. Ueda, "Effects of Additives on piezoelectric and Related Properties of PbTiO_3," Jpn. J. Appl. Phys.[J], 1972, (11): 450～462 (1-4-3)
8．包定华，翟继卫，张良莹，姚熙，“(Pb，Ca)TiO_3纳米晶粉末的溶胶-凝胶合成及表征”，功能材料[J]，1999，30(2)：182～183 11-8
9．傅宏刚，于海涛，张新等，“Ca改性钛酸铅纳米晶的制备及结构研究”，高等学校化学学报[J]，1999，20(8)：1271～1275 11
10. Chen-Chia Chou, Hon-Yi Chang, I-Nan L/N, Bin-Jen SHAW, and Jian-Tao TAN, "Microscopic examination of sintered (Pb_(0.6)Sr_(0.4))TiO_3 positive-temperature-coefficient resistor materials", Jpn. J. Appl. Phys. [J], 1998,37(9B)5269～5272 1-6
11．王得君，郭淳，桂治轮等，“(Sr，Pb)TiO_3陶瓷材料的制备、结构和性质”，硅酸盐学报[J]，1997，25(5)：547～552 13-11
12．龚红宇，范素华，赵宗昱等，“电子陶瓷粉钛酸锶铅的液相合成技术研究”，复合材料学报[J]，1999，16(2)：121～124 12-2
13．朱景川，程华容，尹钟大等，“钛酸锶铅梯度功能陶瓷的显微结构及介电性能”，无机材料学报[J]，2002，17(5)：992～998 12-7
14. Hsiu-Fung Cheng, Chen-Ti Hu, Yen-Yi Lin and I-Nan Lin "Modeling on the resistivity-temperature properties of (Sr_(0.6),Pb_(0.4))TiO_3 materials prepared by the rapid thermal sintering process" Jpn. J. Appl. Phys[J], 1998,37,1932～1938 1-17
15．赵丽丽，王雪文，张志勇等，“溶胶-凝胶制备(Sr，Pb)TiO_3纳米晶粉及表征”，功能材料[J]，2002，33(4)：410～412
16. Chun-Shu Hou, and Chen-Chia Chou, "Fatigue properties and microstructural evolution of Microstructural characteristic of microwave sintered semiconductive (Sr, Pb)TiO_3 ceramics", Feroelectrics [J], 1999,231,25～30 3-2
17. Chen-Chia Chou, Ping-Hong Chen and I-Nan Lin, "Microstructural characteristics of microwave sintered semi-conductive (Sr, Pb)TiO_3 ceramics", Feroelectrics [J], 1999,231,37～42 3-1
18. Ping-Hong Chen, Chen-Chia Chou and Hsiu-Fung Cheng, "Microstructural characteristics and nonequilibrum core-shell phase in (Sr, Pb)TiO_3 materials and their electrical properties", Feroelectrics, 2000, 241, 25～34 3-9
19．王德君，周济，桂治轮，李龙土，“(Sr，Pb)TiO_3超微粉体的制备和性质”，无机材料学报[J]，1996，12(2)：231～236 11-13
20. S. Subrahmanyam, E. Goo, "Diffuse phase transitions in the (Ba, Pb)TiO_3 system", Journal of Materials Science[J], 1998, 33, 4085～4088 4-5
21．吴明媚，李理，徐如人，“(Ba，Pb)TiO_3的水热合成”，化学学报[J]，1996，(54)：1181～8547．
22. L. A. Bassora and J. A. Eiras, "Dielectric relaxation in PLT(Pb_(1-x)la_xTiO_3)ceramics in the microwave region (0.05-2.0 Ghz), Feroelectrics [J], 1999,223,285～292 3-5
23．傅宏刚，张志谦，张新等，“Pb_(1-x)la_xTi_((1-x)/4)O_3纳米晶的结构”，应用化学[J]，2000，17(1)：107～109 11
24．余大书，张明福，韩杰才，“钇掺杂改性PbTiO_3纳米陶瓷介电特性及复阻抗研究”，功能材料[J]，2001，32(1)：72～73
25．惠春，徐爱兰，梁瑞林，“水热合成PZT热电体结晶粉末工艺及相
关性能的研究”，功能材料[J]，1995，26(4)：332～336 (10-2)
26．古映莹，戴恩斌，黄可龙，“水热法制备PZT压电陶瓷粉体”，无机材料学报[J]，1999，14(4)：665～668 (10-1)
27. Stefan Geis, Peer Lobmann, S. Seifert and Jochen Fricke, "dielectric properties of PZT aerogels", Feroelectrics [J],2000,241,75～82 3-7
28. Sheng-Yuan Chu, Chia-Hsin Chen, "Effect of calcium on the piezoelectric and dielectric of Sm-modified PbTiO_3 ceramics", Sensor and Actuators[J], 2001,(89):210～214 1-11
29．唐新桂，周歧发，尹荔松，张进修，“(Pb，Ca，La)TiO_3纳米晶的制备及其表征”，无机材料学报[J]，1998，13(5)：655～659 11-9
30．郭卫红，汪济奎编著。现代功能材料及其应用[M]。北京：化学工业出版社，2002．8，271
31．张祥麟，王曾隽主编。应用无机化学[M]。北京：高等教育出版社，1992，221
32．徐天华，朱云松，“高温钛酸铅PTCR陶瓷制备中铅的挥发与抑制”，功能材料[J]，1996，27(1)：64～66 (11-2)
33．汪晖，薛万荣，陆佩文，沈大为，张其土，“过量氧化铅和氧化铅气氛对改性钛酸铅压电陶瓷机电性能及其微结构的影响”，功能材料[J]，1993，24(6)：533～536 (11-1)
34. Lingbing Kong, Weiguang Zhu and OOI KIANG TAN, "Direct formation of nano-sized PbTiO_3 powders by high energy ball milling", Ferroelectrics[J] 1999, 230,281～286 (2-6)
35．仕国，“超微粉制备技术及其进展”，功能材料[J]，1997，28[3]：237～241
36．徐如人，无机合成化学[M]，北京：高等教育出版社，1991．217～218
37. Chad R. Peterson and Elliott B. Slamovich, "Effect of Parameters on the Morphology of Hydrothermally Derived PbTiO_3 Powders," J.Am. Ceram.Soc.[J], 1999,82(7):1702～1710 1-2
38. M.M. Lencka and R.E. Riman, "Synthesis of Lead Titanate: Thermodynamic Modeling and Experimental Verification," J. AM. Ceram. Soc.[J], 1993,76(10):2649～2659 1-2-6
39. M.M. Lencka and R.E. Riman, "Thermodynamic Modeling of
Hydrothermal Synthesis of Ceramic Powders," Chem. Mater.[J], 1993,5(1):61～70 1-2-7
40．翟学良，“水热法制备四方相BaTiO_3及其晶型转化机理”，硅酸盐学报[J]，2000，28(4)：357～60
41. Jooho Moon, Jeffrey A. Kerchner, Henrik Krarup, and James H. Adair, "Hydrothermal synthesis of ferroelectric perovskites from chemically modified titanium isopropoxide and acetate salts," J. Mater. Res. [J], 1999,14(2):425～435 1-16
42. S.Sato,T.Murakata, H.Yanagi, and F. Miyasaka, "Hydrothermal Synthesis of Fine Perovskite PbTiO_3 Powders with a Simple Mode of Size Distribution," J. Mater[J]. Sol., 1994,(29):5657～5663 1-2-8
43. Dai-rong Chen and Ru-ren Xu, "Hydrothermal synthesis and characterization of perovskite PbTiO_3 powders from different precursors", Chemical Research in Chinese Universities, [J]1998,14(3):225～229
44．郭景坤，“中国先进陶瓷研究及其展望”，材料研究学报[J]，1997，11(6)：594～599
45. J.B. Blum, S. R. Gtrkovich, " Sol-gel-derived PbTiO_3," JOURNAL OF MATERIALS SCIENCE[J], 1985,(20):4479～4483
46. S.R. Gurkovich, J.B. Blum, "CRYSTALLIZATION OF AMORPHOUS LEAD-TITANATE PREPARED BY A SOL-GEL PROCESS," Ferroelectrics. [J] 1985,(62): 189～194
47．路琼华，工科无机化学，华东华工学院出版社，1988．651．
48．李彬，肖红，张维刚，“溶胶凝-胶法合成发光玻璃陶瓷材料的研究”，硅酸盐学报[J]，1990，18(5)：414～421
49．周小微，徐颖，刘国范等，“PbTiO_3纳米晶制备能及表征”，功能材料[J]，1997，28(4)：415～417 11-10
50．王晓慧，汪信，“钛酸铅及掺杂体系纳米材料的晶体结构尺寸效应”，功能材料[J]，1996，27(3)：261～263 11-12
51．刘晓鹏，孟长功，杨大智等，“水热-溶胶凝胶法合成PbTiO_3／NiTi复合工艺研究”，功能材料[J]，2001，32(3)：303～304 10-15
52．赵振国，马季铭，程虎民，羌笛，“化学共沉淀法制备PbTiO_3微粉”，
研究简报[J]，1993，10(2)：99～101
53. K. J. Standly, I. PackiaSelvam, V. Kumar, "Preparation of fine powders of PbTiO_3 derived from organometallic solution", Materials Letters[J], 1999, (40): 118～123 1-9
54. A. V. PRASASA RAO and M. SURESH, "Ph Dependence of Formation of Stoichiometric Precursors for Cadmium and Lead Titanates-a Thermal Study," Ferroelectrics[J], 1999, 229,141～146 2-4
55. Emerson R. Camargo and Masato Kakihana, "Peroxide-Based Route Free from Halides for the Synthesis of Lead Titanate Powder", Chem. Mater. [J] 2001, (113): 1181～1184 1-3
56. E. R. Leite, E. C. Paris, and E. Longo, "Drect amorphous-to-cubic perovskite phase transformation for lead titanate," J. Am. Ceram[J]. Soc., 2000, 83(6): 1539～1541 1-5
57. M. Kakihana, T. Okubo, M. Arima, M. Yashima, and M. Yoshimura, "Polymeric Complex Synthesis of Perovskite Lead Titanate at Reduced Temperature: Possible Formation of Heterometallic (Pb,Ti)-Citric Acid Complex," Chem Mater. [J], 1997, (9): 451～456 1-5-2
58. H. Idrissi, A. Aboujalil, J. P. Deloume, G. Fantozzi and B. Durand, "Molten salt preparation lead titanate: powder characterization, sintering and physical properties", Journal of the European Ceramic Society[J], 1999,(19): 1997～2004 1-8
59．齐利民，马季铭，程虎民，赵振国，“醇盐水解法制备钛酸铅微粉的机理研究”，高等学校化学报[J]，1994，15(12)：1834～1837
60. RBISWAS, G. YANG and M. R. ZACHARIAH, "In situ processing of ferroelectric material from lead waste streams by injection of gas phase titanium precursors: laser indced fluorescence and x-ray diffraction measurements", Cornbust. Sci. and Tech. [J], 1998,134,183～200 2-1
61. X. G. Tang, H. K. Guo, Q. F. Zhou, and J. X. Zhang, "Synthesis and structure of nanocrystalline oxides based on PbTiO_3 by sol-gel process", NanoStructured Materials, [J] 1998, 10(2): 161～168 1-10
62. Yen-Yi Lin and Chen-Ti Hu, "Electrical properties of the positive temperature coefficent of resistivity materials with 490℃ critical
temperature", J.Appl. Phys. [J] 1998,83(3): 1321～1326 1-12
63. Hsiu-Fung CHENG, Chen-Ti HU, Yen-Yi LIN, and I-Nan LIN, "Modeling on resistivity-temperature properties of (Pb_(0.6)Sr_(0.4))TiO_3 materials prepared by the rapid thermal sintering process", Jpn. J. Appl. Phys. [J], 1998, (37), 1932～1938 1-17
64．李翰如编著。电介质物理导论[M]。成都科技大学出版社，1990，1～279
65．周达飞主编。材料概论[M]。化学工业出版社，2001．7
66．孙酣经，黄澄华主编。化工新材料产品及应用手册[M]。北京：中国石化出版社，2002．1，1227
67．万学华，戴黎明，张火荣，“钛酸铅材料温度系数的改善”，压电与声光[J]，1999，21(3)：219～223
68．熊荣，程虎民，马季铭等，“稀土改性钛酸铅微粉的水热合成及其性能研究”，高等学校化学学报[J]，199718(10)1580～1584
69．洪广言。无机固体化学[M]。北京：科学出版社，2002．7
70．北京师范大学，华中师范大学，南京师范大学。无机化学[M](上册)。北京：高等教育出版社，1992．9
71．何元金，马兴坤，桂治轮，李龙土，“用正电子湮没研究钙钛矿结构压电陶瓷中的点缺陷”，物理学报[J]，1998，47(1)：146～153
72．熊兆贤。陶瓷材料的分形研究[M]。北京：科学出版社，2000．221-223
73．赵鹏，姚熹，翟继卫，张德生，张良莹，“溶胶-凝胶法制备PbTiO_3铁电玻璃陶瓷的高频晶粒尺寸效应”， 材料研究学报[J]，2000，14(3)：234～237
74. Wang D J, Gui Z L, Li L T. J. Mater. Sci.: Materials in Electrics, 1997, 8:271～276
75. Chen-Chia Chou, et al. Jpn. J. Appl. Phys., 1998,37:5269～5272
76．李鄂胜，陈华毅，连俊杰．电子元件与材料，1990，9(5)：50～54．
77. Wang D J, et al. Mater. Lett., 1997, 30(4):275～277
78. Chang H Y, et al. Mater. Chem. And Phys., 1995,42:258～263
79．王茂祥，孙彤，孙平，“(Pb_(1-x)，Sr_x)TiO_3系红外敏感铁电陶瓷的研究”，应用科学学报[J]，2000，18(4)：365～367
80. H. M. Chan, M. P. Harmer, D. M. Smyth, Mater. Soc. Symp. Proc., 1984,31:345
81．王永龄。功能陶瓷性能与应用[M]。北京：科学技术出版社，2003．2，98
82. Ka Kegawa K, Mouri J. J Am Ceram. Soc, 1985,68:204
83. Kutty T R N, Banchandran R. Mater Res Bull, 1984,19:1479～1488
84．濑升等著，赵修建等译。超微颗粒导论[M]。武汉：武汉工业大学，1991。
85. Noboru Tohge, et al. J. Am. Ceram. Soc., 1991,74(1):67～71
86. Ulagaraj, et al. J. Am. Ceram. Sot., 1993, 76(6):1441～1444
87．钟维烈。铁电体物理学[M]。北京：科学技术出版社，2000．6，22～26
88．高濂，李蔚。纳米陶瓷[M]。北京：化学工业出版社，2002．1，50～55
2. Tomonari Takeuchi, Mitsuharu Tabuchi, Isao Kondoh, Nobuyuki Tamari, and Hiroyuki Kageyama, "Synthesis of Dense Lead Titanate Ceramics with Submicrometer Grains by Spark Plasma Sintering," J. Am. Ceram. Soc[J]., 2000, 83 (3): 541-544. (1-4)
3. Ji-wei Zhai, Xi Yao, Ming-zhang Wu et al., "Preparation and microwave characterization of PbTiO_3 ceramic and powder," J. Phys. D: Appl. Phys.[J], 2001, (34): 1413～1416 (1-1)
4．江东亮等编。精细陶瓷材料[M]。中国物资出版社，2000．214
5．熊家林，贡长生，张可立主编，无机精细化学品的制备与应用[M]，化学工业出版社．1999．305～312
6. Jun-min Xue, Dong-mei Wan, John Wang et al., "Mechanochemical synthesis of nanosized lead titanate powders from oxides," Materials Letters. [J] , 1999, (39): 364～369 (1-7)
7. Ueda, "Effects of Additives on piezoelectric and Related Properties of PbTiO_3," Jpn. J. Appl. Phys.[J], 1972, (11): 450～462 (1-4-3)
8．包定华，翟继卫，张良莹，姚熙，“(Pb，Ca)TiO_3纳米晶粉末的溶胶-凝胶合成及表征”，功能材料[J]，1999，30(2)：182～183 11-8
9．傅宏刚，于海涛，张新等，“Ca改性钛酸铅纳米晶的制备及结构研究”，高等学校化学学报[J]，1999，20(8)：1271～1275 11
10. Chen-Chia Chou, Hon-Yi Chang, I-Nan L/N, Bin-Jen SHAW, and Jian-Tao TAN, "Microscopic examination of sintered (Pb_(0.6)Sr_(0.4))TiO_3 positive-temperature-coefficient resistor materials", Jpn. J. Appl. Phys. [J], 1998,37(9B)5269～5272 1-6
11．王得君，郭淳，桂治轮等，“(Sr，Pb)TiO_3陶瓷材料的制备、结构和性质”，硅酸盐学报[J]，1997，25(5)：547～552 13-11
12．龚红宇，范素华，赵宗昱等，“电子陶瓷粉钛酸锶铅的液相合成技术研究”，复合材料学报[J]，1999，16(2)：121～124 12-2
13．朱景川，程华容，尹钟大等，“钛酸锶铅梯度功能陶瓷的显微结构及介电性能”，无机材料学报[J]，2002，17(5)：992～998 12-7
14. Hsiu-Fung Cheng, Chen-Ti Hu, Yen-Yi Lin and I-Nan Lin "Modeling on the resistivity-temperature properties of (Sr_(0.6),Pb_(0.4))TiO_3 materials prepared by the rapid thermal sintering process" Jpn. J. Appl. Phys[J], 1998,37,1932～1938 1-17
15．赵丽丽，王雪文，张志勇等，“溶胶-凝胶制备(Sr，Pb)TiO_3纳米晶粉及表征”，功能材料[J]，2002，33(4)：410～412
16. Chun-Shu Hou, and Chen-Chia Chou, "Fatigue properties and microstructural evolution of Microstructural characteristic of microwave sintered semiconductive (Sr, Pb)TiO_3 ceramics", Feroelectrics [J], 1999,231,25～30 3-2
17. Chen-Chia Chou, Ping-Hong Chen and I-Nan Lin, "Microstructural characteristics of microwave sintered semi-conductive (Sr, Pb)TiO_3 ceramics", Feroelectrics [J], 1999,231,37～42 3-1
18. Ping-Hong Chen, Chen-Chia Chou and Hsiu-Fung Cheng, "Microstructural characteristics and nonequilibrum core-shell phase in (Sr, Pb)TiO_3 materials and their electrical properties", Feroelectrics, 2000, 241, 25～34 3-9
19．王德君，周济，桂治轮，李龙土，“(Sr，Pb)TiO_3超微粉体的制备和性质”，无机材料学报[J]，1996，12(2)：231～236 11-13
20. S. Subrahmanyam, E. Goo, "Diffuse phase transitions in the (Ba, Pb)TiO_3 system", Journal of Materials Science[J], 1998, 33, 4085～4088 4-5
21．吴明媚，李理，徐如人，“(Ba，Pb)TiO_3的水热合成”，化学学报[J]，1996，(54)：1181～8547．
22. L. A. Bassora and J. A. Eiras, "Dielectric relaxation in PLT(Pb_(1-x)la_xTiO_3)ceramics in the microwave region (0.05-2.0 Ghz), Feroelectrics [J], 1999,223,285～292 3-5
23．傅宏刚，张志谦，张新等，“Pb_(1-x)la_xTi_((1-x)/4)O_3纳米晶的结构”，应用化学[J]，2000，17(1)：107～109 11
24．余大书，张明福，韩杰才，“钇掺杂改性PbTiO_3纳米陶瓷介电特性及复阻抗研究”，功能材料[J]，2001，32(1)：72～73
25．惠春，徐爱兰，梁瑞林，“水热合成PZT热电体结晶粉末工艺及相
关性能的研究”，功能材料[J]，1995，26(4)：332～336 (10-2)
26．古映莹，戴恩斌，黄可龙，“水热法制备PZT压电陶瓷粉体”，无机材料学报[J]，1999，14(4)：665～668 (10-1)
27. Stefan Geis, Peer Lobmann, S. Seifert and Jochen Fricke, "dielectric properties of PZT aerogels", Feroelectrics [J],2000,241,75～82 3-7
28. Sheng-Yuan Chu, Chia-Hsin Chen, "Effect of calcium on the piezoelectric and dielectric of Sm-modified PbTiO_3 ceramics", Sensor and Actuators[J], 2001,(89):210～214 1-11
29．唐新桂，周歧发，尹荔松，张进修，“(Pb，Ca，La)TiO_3纳米晶的制备及其表征”，无机材料学报[J]，1998，13(5)：655～659 11-9
30．郭卫红，汪济奎编著。现代功能材料及其应用[M]。北京：化学工业出版社，2002．8，271
31．张祥麟，王曾隽主编。应用无机化学[M]。北京：高等教育出版社，1992，221
32．徐天华，朱云松，“高温钛酸铅PTCR陶瓷制备中铅的挥发与抑制”，功能材料[J]，1996，27(1)：64～66 (11-2)
33．汪晖，薛万荣，陆佩文，沈大为，张其土，“过量氧化铅和氧化铅气氛对改性钛酸铅压电陶瓷机电性能及其微结构的影响”，功能材料[J]，1993，24(6)：533～536 (11-1)
34. Lingbing Kong, Weiguang Zhu and OOI KIANG TAN, "Direct formation of nano-sized PbTiO_3 powders by high energy ball milling", Ferroelectrics[J] 1999, 230,281～286 (2-6)
35．仕国，“超微粉制备技术及其进展”，功能材料[J]，1997，28[3]：237～241
36．徐如人，无机合成化学[M]，北京：高等教育出版社，1991．217～218
37. Chad R. Peterson and Elliott B. Slamovich, "Effect of Parameters on the Morphology of Hydrothermally Derived PbTiO_3 Powders," J.Am. Ceram.Soc.[J], 1999,82(7):1702～1710 1-2
38. M.M. Lencka and R.E. Riman, "Synthesis of Lead Titanate: Thermodynamic Modeling and Experimental Verification," J. AM. Ceram. Soc.[J], 1993,76(10):2649～2659 1-2-6
39. M.M. Lencka and R.E. Riman, "Thermodynamic Modeling of
Hydrothermal Synthesis of Ceramic Powders," Chem. Mater.[J], 1993,5(1):61～70 1-2-7
40．翟学良，“水热法制备四方相BaTiO_3及其晶型转化机理”，硅酸盐学报[J]，2000，28(4)：357～60
41. Jooho Moon, Jeffrey A. Kerchner, Henrik Krarup, and James H. Adair, "Hydrothermal synthesis of ferroelectric perovskites from chemically modified titanium isopropoxide and acetate salts," J. Mater. Res. [J], 1999,14(2):425～435 1-16
42. S.Sato,T.Murakata, H.Yanagi, and F. Miyasaka, "Hydrothermal Synthesis of Fine Perovskite PbTiO_3 Powders with a Simple Mode of Size Distribution," J. Mater[J]. Sol., 1994,(29):5657～5663 1-2-8
43. Dai-rong Chen and Ru-ren Xu, "Hydrothermal synthesis and characterization of perovskite PbTiO_3 powders from different precursors", Chemical Research in Chinese Universities, [J]1998,14(3):225～229
44．郭景坤，“中国先进陶瓷研究及其展望”，材料研究学报[J]，1997，11(6)：594～599
45. J.B. Blum, S. R. Gtrkovich, " Sol-gel-derived PbTiO_3," JOURNAL OF MATERIALS SCIENCE[J], 1985,(20):4479～4483
46. S.R. Gurkovich, J.B. Blum, "CRYSTALLIZATION OF AMORPHOUS LEAD-TITANATE PREPARED BY A SOL-GEL PROCESS," Ferroelectrics. [J] 1985,(62): 189～194
47．路琼华，工科无机化学，华东华工学院出版社，1988．651．
48．李彬，肖红，张维刚，“溶胶凝-胶法合成发光玻璃陶瓷材料的研究”，硅酸盐学报[J]，1990，18(5)：414～421
49．周小微，徐颖，刘国范等，“PbTiO_3纳米晶制备能及表征”，功能材料[J]，1997，28(4)：415～417 11-10
50．王晓慧，汪信，“钛酸铅及掺杂体系纳米材料的晶体结构尺寸效应”，功能材料[J]，1996，27(3)：261～263 11-12
51．刘晓鹏，孟长功，杨大智等，“水热-溶胶凝胶法合成PbTiO_3／NiTi复合工艺研究”，功能材料[J]，2001，32(3)：303～304 10-15
52．赵振国，马季铭，程虎民，羌笛，“化学共沉淀法制备PbTiO_3微粉”，
研究简报[J]，1993，10(2)：99～101
53. K. J. Standly, I. PackiaSelvam, V. Kumar, "Preparation of fine powders of PbTiO_3 derived from organometallic solution", Materials Letters[J], 1999, (40): 118～123 1-9
54. A. V. PRASASA RAO and M. SURESH, "Ph Dependence of Formation of Stoichiometric Precursors for Cadmium and Lead Titanates-a Thermal Study," Ferroelectrics[J], 1999, 229,141～146 2-4
55. Emerson R. Camargo and Masato Kakihana, "Peroxide-Based Route Free from Halides for the Synthesis of Lead Titanate Powder", Chem. Mater. [J] 2001, (113): 1181～1184 1-3
56. E. R. Leite, E. C. Paris, and E. Longo, "Drect amorphous-to-cubic perovskite phase transformation for lead titanate," J. Am. Ceram[J]. Soc., 2000, 83(6): 1539～1541 1-5
57. M. Kakihana, T. Okubo, M. Arima, M. Yashima, and M. Yoshimura, "Polymeric Complex Synthesis of Perovskite Lead Titanate at Reduced Temperature: Possible Formation of Heterometallic (Pb,Ti)-Citric Acid Complex," Chem Mater. [J], 1997, (9): 451～456 1-5-2
58. H. Idrissi, A. Aboujalil, J. P. Deloume, G. Fantozzi and B. Durand, "Molten salt preparation lead titanate: powder characterization, sintering and physical properties", Journal of the European Ceramic Society[J], 1999,(19): 1997～2004 1-8
59．齐利民，马季铭，程虎民，赵振国，“醇盐水解法制备钛酸铅微粉的机理研究”，高等学校化学报[J]，1994，15(12)：1834～1837
60. RBISWAS, G. YANG and M. R. ZACHARIAH, "In situ processing of ferroelectric material from lead waste streams by injection of gas phase titanium precursors: laser indced fluorescence and x-ray diffraction measurements", Cornbust. Sci. and Tech. [J], 1998,134,183～200 2-1
61. X. G. Tang, H. K. Guo, Q. F. Zhou, and J. X. Zhang, "Synthesis and structure of nanocrystalline oxides based on PbTiO_3 by sol-gel process", NanoStructured Materials, [J] 1998, 10(2): 161～168 1-10
62. Yen-Yi Lin and Chen-Ti Hu, "Electrical properties of the positive temperature coefficent of resistivity materials with 490℃ critical
temperature", J.Appl. Phys. [J] 1998,83(3): 1321～1326 1-12
63. Hsiu-Fung CHENG, Chen-Ti HU, Yen-Yi LIN, and I-Nan LIN, "Modeling on resistivity-temperature properties of (Pb_(0.6)Sr_(0.4))TiO_3 materials prepared by the rapid thermal sintering process", Jpn. J. Appl. Phys. [J], 1998, (37), 1932～1938 1-17
64．李翰如编著。电介质物理导论[M]。成都科技大学出版社，1990，1～279
65．周达飞主编。材料概论[M]。化学工业出版社，2001．7
66．孙酣经，黄澄华主编。化工新材料产品及应用手册[M]。北京：中国石化出版社，2002．1，1227
67．万学华，戴黎明，张火荣，“钛酸铅材料温度系数的改善”，压电与声光[J]，1999，21(3)：219～223
68．熊荣，程虎民，马季铭等，“稀土改性钛酸铅微粉的水热合成及其性能研究”，高等学校化学学报[J]，199718(10)1580～1584
69．洪广言。无机固体化学[M]。北京：科学出版社，2002．7
70．北京师范大学，华中师范大学，南京师范大学。无机化学[M](上册)。北京：高等教育出版社，1992．9
71．何元金，马兴坤，桂治轮，李龙土，“用正电子湮没研究钙钛矿结构压电陶瓷中的点缺陷”，物理学报[J]，1998，47(1)：146～153
72．熊兆贤。陶瓷材料的分形研究[M]。北京：科学出版社，2000．221-223
73．赵鹏，姚熹，翟继卫，张德生，张良莹，“溶胶-凝胶法制备PbTiO_3铁电玻璃陶瓷的高频晶粒尺寸效应”， 材料研究学报[J]，2000，14(3)：234～237
74. Wang D J, Gui Z L, Li L T. J. Mater. Sci.: Materials in Electrics, 1997, 8:271～276
75. Chen-Chia Chou, et al. Jpn. J. Appl. Phys., 1998,37:5269～5272
76．李鄂胜，陈华毅，连俊杰．电子元件与材料，1990，9(5)：50～54．
77. Wang D J, et al. Mater. Lett., 1997, 30(4):275～277
78. Chang H Y, et al. Mater. Chem. And Phys., 1995,42:258～263
79．王茂祥，孙彤，孙平，“(Pb_(1-x)，Sr_x)TiO_3系红外敏感铁电陶瓷的研究”，应用科学学报[J]，2000，18(4)：365～367
80. H. M. Chan, M. P. Harmer, D. M. Smyth, Mater. Soc. Symp. Proc., 1984,31:345
81．王永龄。功能陶瓷性能与应用[M]。北京：科学技术出版社，2003．2，98
82. Ka Kegawa K, Mouri J. J Am Ceram. Soc, 1985,68:204
83. Kutty T R N, Banchandran R. Mater Res Bull, 1984,19:1479～1488
84．濑升等著，赵修建等译。超微颗粒导论[M]。武汉：武汉工业大学，1991。
85. Noboru Tohge, et al. J. Am. Ceram. Soc., 1991,74(1):67～71
86. Ulagaraj, et al. J. Am. Ceram. Sot., 1993, 76(6):1441～1444
87．钟维烈。铁电体物理学[M]。北京：科学技术出版社，2000．6，22～26
88．高濂，李蔚。纳米陶瓷[M]。北京：化学工业出版社，2002．1，50～55