稀土铌酸系列陶瓷的合成及介电性能研究
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摘要
近年来，随着环境对材料无铅化的不断需求，新型功能材料包括微波介质材料、压电和铁电材料逐渐成为人们研究的热点。稀土铌酸系列陶瓷LnNbO_4(Ln代表La至Lu包含Y的稀土元素)属于类钙钛矿白钨矿结构(ABO_3)，是一类结构和相变特性相似的新型微波介质陶瓷材料，其A位和B位离子可被半径和电价不同的各种元素离子在一定浓度范围内单独或复合取代，从而可以在比较大的范围内调节材料性能以适应不同场合的应用。本论文分别以重稀土元素镱(Yb)、轻稀土元素铈(Ce)为代表替代A位离子，结合前期合成制备的YNbO_4，研究这一系列陶瓷的制备工艺、显微结构与介电性能的关系等问题。
以Yb_2O_3、Nb_2O_5为原料，按摩尔比Yb_2O_3：Nb_2O_5=1：1的比例在无保护气氛下氧化烧结，采用两种工艺——经预烧结后二次烧结和直接原位合成，对比得出了采用前者能烧结制得比较致密的陶瓷体，其中在136℃得到的YbNbO_4陶瓷的介电常数为23，品质因数Q值达到3．38x10~4。
以Bi_2O_3为助剂掺杂烧结YbNbO_4，从烧结温度、掺杂量方面研究了Bi_2O_3掺杂对YbNbO_4的烧结行为、相结构、显微形貌及其介电性能的影响。掺杂Bi_2O_3后，能一定程度降低YbNbO_4烧结温度，但对微波介电性能的影响不明显。
以CeO_2、Nb_2O_5为原料，分别按摩尔比CeO_2：Nb_2O_5=1：1和CeO_2：Nb_2O_5=2：1的比例在无保护气氛下常压烧结，原位合成了铌酸铈陶瓷体，研究了其相结构随温度的转变(CeNbO_(4+δ)(δ=0～0．25))、显微形貌和介电性能的特点。
In recent years, with the increasing demand of lead-free and environmental materials, new types of communication function materials including dielectric, piezoelectric and ferroelectric materials are in the focus of people's researches. Rare-earth niobate ceramics with general formula LnNbO_4(Ln represent La to Lu including Y) is a series of new functional microwave dielectric ceramic materials ,which has a ferroelastic phase of monoclinic structure at ambient temperature with similar structural phase transition characteristics, belongs to the perovskite scheelite class(ABO_3). Their location of A or B can be replaced by other hydroniums with different radius and electrovalency to a certain extent, individually or in the compound. Thus, we can regulate the properties of material for different use. This paper is focus on replacing the location A with Yb or Ce, adding YNbO_4 synthesized before, preliminary study their synthesize technology, microscopic structure and dielectric properties of relations and so on.
The main raw materials applied are ytterbium oxide (Yb_2O_3) and niobium oxide (Nb_2O_5). YbNbO_4 were obtained with molar rate of Yb_2O_3:Nb_2O_5=1:1, sintering of non-protected atmosphere through two technics "pre-sintering and then second sintering" and "In-situ synthesis". We obtained YbNbO_4 ceramic with dielectric constant 26, Q value of 3.38×104 at sintering temperature 1360℃.
Doped with Bi_2O_3, YbNbO_4 were studied on its sintering behavior, crystal structure and dielectric properties. The results showed that the sintering temperature is lowed to some extent, yet the influence of Bi_2O_3 to the dielectric properties is not very obvious.
Next, using the cerium oxide (CeO_2) and niobium oxide (Nb_2O_5), we got the ceramics of CeNbO_(4+δ) (δ=0-0.25) and some unknown phases with the molar rate of CeO_2 :Nb_2O_5=1:1 and CeO_2 :Nb_2O_5=2:1. CeNbO_(4+δ) is very sensitive to environmental oxygen. Their crystal transformation, microstructure and change of dielectric properties were investigated.
以Yb_2O_3、Nb_2O_5为原料，按摩尔比Yb_2O_3：Nb_2O_5=1：1的比例在无保护气氛下氧化烧结，采用两种工艺——经预烧结后二次烧结和直接原位合成，对比得出了采用前者能烧结制得比较致密的陶瓷体，其中在136℃得到的YbNbO_4陶瓷的介电常数为23，品质因数Q值达到3．38x10~4。
以Bi_2O_3为助剂掺杂烧结YbNbO_4，从烧结温度、掺杂量方面研究了Bi_2O_3掺杂对YbNbO_4的烧结行为、相结构、显微形貌及其介电性能的影响。掺杂Bi_2O_3后，能一定程度降低YbNbO_4烧结温度，但对微波介电性能的影响不明显。
以CeO_2、Nb_2O_5为原料，分别按摩尔比CeO_2：Nb_2O_5=1：1和CeO_2：Nb_2O_5=2：1的比例在无保护气氛下常压烧结，原位合成了铌酸铈陶瓷体，研究了其相结构随温度的转变(CeNbO_(4+δ)(δ=0～0．25))、显微形貌和介电性能的特点。
In recent years, with the increasing demand of lead-free and environmental materials, new types of communication function materials including dielectric, piezoelectric and ferroelectric materials are in the focus of people's researches. Rare-earth niobate ceramics with general formula LnNbO_4(Ln represent La to Lu including Y) is a series of new functional microwave dielectric ceramic materials ,which has a ferroelastic phase of monoclinic structure at ambient temperature with similar structural phase transition characteristics, belongs to the perovskite scheelite class(ABO_3). Their location of A or B can be replaced by other hydroniums with different radius and electrovalency to a certain extent, individually or in the compound. Thus, we can regulate the properties of material for different use. This paper is focus on replacing the location A with Yb or Ce, adding YNbO_4 synthesized before, preliminary study their synthesize technology, microscopic structure and dielectric properties of relations and so on.
The main raw materials applied are ytterbium oxide (Yb_2O_3) and niobium oxide (Nb_2O_5). YbNbO_4 were obtained with molar rate of Yb_2O_3:Nb_2O_5=1:1, sintering of non-protected atmosphere through two technics "pre-sintering and then second sintering" and "In-situ synthesis". We obtained YbNbO_4 ceramic with dielectric constant 26, Q value of 3.38×104 at sintering temperature 1360℃.
Doped with Bi_2O_3, YbNbO_4 were studied on its sintering behavior, crystal structure and dielectric properties. The results showed that the sintering temperature is lowed to some extent, yet the influence of Bi_2O_3 to the dielectric properties is not very obvious.
Next, using the cerium oxide (CeO_2) and niobium oxide (Nb_2O_5), we got the ceramics of CeNbO_(4+δ) (δ=0-0.25) and some unknown phases with the molar rate of CeO_2 :Nb_2O_5=1:1 and CeO_2 :Nb_2O_5=2:1. CeNbO_(4+δ) is very sensitive to environmental oxygen. Their crystal transformation, microstructure and change of dielectric properties were investigated.
引文
[1]千福熹．信息材料．天津大学出版社，2000，200-222
[2]徐郑，倪宏伟．现代功能陶瓷．北京．国防工业出版社，1998．9
[3]赵连泽．新型材料学导论．南京：南京大学出版社，2000．4
[4]张迎春．铌钽酸盐微波介质陶陶瓷．北京．科学出版社：2005
[5]Richtmyer R．D．Didecttic resonatom[J]．J．Appl．phys．1939，10：391-398
[6]尹雪帆，喻佑华等．微波介质陶瓷材料发展综述．中国陶瓷．2006，42(4)
[7]龚艳，肖奇，张清岑．微波介质陶瓷的研究进展．材料导报．2004，18(11)：70-72
[8]张绪礼．电介质物理与微波介质陶瓷．压电与声电．1997，19(5)：29-33
[9]张绪礼，王莜珍，汤清华．微波介质陶瓷与器件．电子科技导报．1997，(6)：315-320
[10]Konishi Y．Novel dielectric waveguide components-microwave applications of new ceramic materials．Proceedings of the IEEE．1991，79(6)：726-740
[11]朱建华，粱飞，汪小红，吕文中．微波介质陶瓷材料介电性能间的制约关系，电子元件 与材料，2005，3(3)：32-33
[12]尹艳红，刘维平．微波介质陶瓷及其发展趋势．冶金丛刊，2006，163(3)：41-44
[13]李言荣，恽正中，电子材料导论．北京．清华大学出版社，2001：245-248
[14]B．W．Hakki，P．D．Coleman，A Dielectric Resonator Method of Measuring Inductive Capacities in the Millimeter Range，IRE Transactions on Microwave Theory and Techniques，MTT-8，(1960 July)：402-409
[15]Wolfram Wersing．Microwave ceramics for resonators and filters，Current Opinion in Solid State & Materials Science，1996，1(5)：715-731
[16]石锋．Ba(Zn_(1/3)Nb_(2／3))O_3微波介质陶瓷介电性能的研究．天津大学．2003
[17]何进．微波陶瓷材料．电于元件与材料．1995，14(2)：7-13
[18]周水杉．微波介质陶瓷材料的发展．电子元件与材料．1988，7(2)：8-12
[19]徐廷献．电子陶瓷材料．天津大学出版社，1992
[20]Wakino K，Nishikawa T，Ishikawa Y and Tamura H．Dielectric resonator materials and their applications for mobile communication systems．Br．Ceram．Trans．J．1990，89(2)：39-43
[21]高春华，黄新友．微波介质陶瓷及其展望．陶瓷．2002，(1)：42-45
[22]郑兴华，俞建长，汤德平．高介电常数微波介质陶瓷．山东陶瓷．2004，27(6)：28-32
[23]Venkatesh J．Sivasubramanian V．Subramanian V et al．Far—IR Reflectance Study on B-sice Disordered Ba(Zn_(1／3)Ta_(2／3))O_3 Dielectric Resonator[J]．Materials Research Bulletin，2000(35)： 1325-1332
[24]Tien L C，Chou C C．Tsai D S．Ordered Structure and Dielectric Properties of Lanthanum—substituted Ba(Mg_(1／3)Ta_(2／3))O_3[J]．J．Am．Ceram．Soc．2000，83(8)：2074-2078
[25]Chen X M，Wu Y J．Effects of NaF upon Sintering Temperature of Ba(Mg_(1／3)Ta_(2／3))O_3 DieLectric Ceramics[J]．J Materials Science：Materials in Electronics，1996(7)：427-431
[26]Rase D E．Roy R．Phase equilibria in the system BaO-TiO_2．J Am Ceram Soc，1955，38： 102
[27] J．K Ploude，C L．Ren，Application of dielectric resonators in microwave components．IEEE??Trans．Microwave Theory Tech．1981．MT-129(8)：754-770
[28]韩家平，张绪礼，王筱珍等．BaO-TiO_2系中Ba_2Ti_9O_(20)相形成的研究．硅酸盐学报[J]， 1996，24(2)：173-178
[29]陈国华．微波介质陶瓷的研究现状及展望．佛山陶瓷．2004，(6)：6-9
[30]郑兴华，梁炳亮．微波介质陶瓷．2005，38(2)：11-15
[31]旧文中，张道礼，黎步银等．高ε_r微波介质陶瓷的结构、介电性质及其研究进展[J]．功 能材料，2000，31(6)：572-576
[32]吴昊．含稀土微波介质陶瓷材料的研究进展．江西有色金属．2004，18(3)：39-43
[33]曲秀荣，贾德昌．微波介质陶瓷的研究进展．硅酸盐通报．2006，25(6)：144-147
[34]胡长征，张辉等．类钙钛矿新铌酸盐Ba_4LaTiNb_3O_(15)的合成、结构与介电性能．无机化学 学报，2006年6月第6期
[35]张绪礼，王淑珍，汤清华．微波介质陶瓷材料与器件新材料新技术．1997年，第6期：29-33
[36]方亮，杨卫明等．微波介质陶瓷的研究现状与发展趋势．武汉理工大学学报．2002，24(2)， 12-15
[37]刘秋平．YNbO_4的合成制备及其介电性能的研究．北京交通大学．2007
[38]刘光华．稀土固体材料学．北京．机械工业出版社．1996，1-37
[39]周焕福，黄金亮．Y~(3+)取代Bi~(3+)的Bi_2O_3-ZnO-Nb_2O_5基陶瓷的结构与介电性．材料导报．2004， 18(11)：84-86
[40] Hakki B W and Coleman P D. A dielectric resonator method of measuring inductive capacitiesin the millimeter range. IEEE. Trans. MTT. 1960, 8:402-410
[41] Kim DW, Ko K H and Hong K S. Influence of Copper(Ⅱ) oxide additions to Zinc Niobatemicrowave ceramic sintering temperature and dielectric properties. J. Am. Ceram. Soc. 2001,84(6): 1286-1290
[42]黄永峰，李谦，黄金亮，龙永强．Bi_2O_3掺入对CLST微波介质陶瓷性能的影响．电子 元件与材料．2006年，第12期
[43] Solomon S, Santha N, Jawahar I N, et al. Tailoring the microwave dielectric properties ofBaRe_2Ti_4O_(12) and BaRe_2Ti_5O_(14) ceramics by compositional variations [J]. J Mater Sci: Materialsin Eletronics, 2000,11(8): 595-602
[44] Hu M Z, Zhou D X, Gu H S, et al. Influence of Bi_2O_3 and MnO_2 doping on microwaveproperties of [(Pb,Ca) La](Fe,Nb)O_3 dielectric ceramics[J]. Mater Sci Eng B, 2005,117(2):199-204
[45] John G. Thompson and Ray L. Withers. Modulated Structures in Oxidized CeriumNiobates. Journal of Solid State Chemistry 143:122-131 (1999)
[46] S.J. Skinner, Y. Kang, X-ray diffraction studies and phase transformations of CeNbO_(4+δ) using insitu techniques, Solid State Science 5(2003): 1475-1479
[47] R.J. Packer,E.V. Tsipis, et.al., Diffusion and conductivity properties of cerium niobate, SolidState Ionics 177(2006):2059-2064
[48] A.A Yaremchenko, et.al. Methane oxidation by lattice oxygen of CeNbO_(4+δ), CatalysisCommunications 8(2007): 335-339
[2]徐郑，倪宏伟．现代功能陶瓷．北京．国防工业出版社，1998．9
[3]赵连泽．新型材料学导论．南京：南京大学出版社，2000．4
[4]张迎春．铌钽酸盐微波介质陶陶瓷．北京．科学出版社：2005
[5]Richtmyer R．D．Didecttic resonatom[J]．J．Appl．phys．1939，10：391-398
[6]尹雪帆，喻佑华等．微波介质陶瓷材料发展综述．中国陶瓷．2006，42(4)
[7]龚艳，肖奇，张清岑．微波介质陶瓷的研究进展．材料导报．2004，18(11)：70-72
[8]张绪礼．电介质物理与微波介质陶瓷．压电与声电．1997，19(5)：29-33
[9]张绪礼，王莜珍，汤清华．微波介质陶瓷与器件．电子科技导报．1997，(6)：315-320
[10]Konishi Y．Novel dielectric waveguide components-microwave applications of new ceramic materials．Proceedings of the IEEE．1991，79(6)：726-740
[11]朱建华，粱飞，汪小红，吕文中．微波介质陶瓷材料介电性能间的制约关系，电子元件 与材料，2005，3(3)：32-33
[12]尹艳红，刘维平．微波介质陶瓷及其发展趋势．冶金丛刊，2006，163(3)：41-44
[13]李言荣，恽正中，电子材料导论．北京．清华大学出版社，2001：245-248
[14]B．W．Hakki，P．D．Coleman，A Dielectric Resonator Method of Measuring Inductive Capacities in the Millimeter Range，IRE Transactions on Microwave Theory and Techniques，MTT-8，(1960 July)：402-409
[15]Wolfram Wersing．Microwave ceramics for resonators and filters，Current Opinion in Solid State & Materials Science，1996，1(5)：715-731
[16]石锋．Ba(Zn_(1/3)Nb_(2／3))O_3微波介质陶瓷介电性能的研究．天津大学．2003
[17]何进．微波陶瓷材料．电于元件与材料．1995，14(2)：7-13
[18]周水杉．微波介质陶瓷材料的发展．电子元件与材料．1988，7(2)：8-12
[19]徐廷献．电子陶瓷材料．天津大学出版社，1992
[20]Wakino K，Nishikawa T，Ishikawa Y and Tamura H．Dielectric resonator materials and their applications for mobile communication systems．Br．Ceram．Trans．J．1990，89(2)：39-43
[21]高春华，黄新友．微波介质陶瓷及其展望．陶瓷．2002，(1)：42-45
[22]郑兴华，俞建长，汤德平．高介电常数微波介质陶瓷．山东陶瓷．2004，27(6)：28-32
[23]Venkatesh J．Sivasubramanian V．Subramanian V et al．Far—IR Reflectance Study on B-sice Disordered Ba(Zn_(1／3)Ta_(2／3))O_3 Dielectric Resonator[J]．Materials Research Bulletin，2000(35)： 1325-1332
[24]Tien L C，Chou C C．Tsai D S．Ordered Structure and Dielectric Properties of Lanthanum—substituted Ba(Mg_(1／3)Ta_(2／3))O_3[J]．J．Am．Ceram．Soc．2000，83(8)：2074-2078
[25]Chen X M，Wu Y J．Effects of NaF upon Sintering Temperature of Ba(Mg_(1／3)Ta_(2／3))O_3 DieLectric Ceramics[J]．J Materials Science：Materials in Electronics，1996(7)：427-431
[26]Rase D E．Roy R．Phase equilibria in the system BaO-TiO_2．J Am Ceram Soc，1955，38： 102
[27] J．K Ploude，C L．Ren，Application of dielectric resonators in microwave components．IEEE??Trans．Microwave Theory Tech．1981．MT-129(8)：754-770
[28]韩家平，张绪礼，王筱珍等．BaO-TiO_2系中Ba_2Ti_9O_(20)相形成的研究．硅酸盐学报[J]， 1996，24(2)：173-178
[29]陈国华．微波介质陶瓷的研究现状及展望．佛山陶瓷．2004，(6)：6-9
[30]郑兴华，梁炳亮．微波介质陶瓷．2005，38(2)：11-15
[31]旧文中，张道礼，黎步银等．高ε_r微波介质陶瓷的结构、介电性质及其研究进展[J]．功 能材料，2000，31(6)：572-576
[32]吴昊．含稀土微波介质陶瓷材料的研究进展．江西有色金属．2004，18(3)：39-43
[33]曲秀荣，贾德昌．微波介质陶瓷的研究进展．硅酸盐通报．2006，25(6)：144-147
[34]胡长征，张辉等．类钙钛矿新铌酸盐Ba_4LaTiNb_3O_(15)的合成、结构与介电性能．无机化学 学报，2006年6月第6期
[35]张绪礼，王淑珍，汤清华．微波介质陶瓷材料与器件新材料新技术．1997年，第6期：29-33
[36]方亮，杨卫明等．微波介质陶瓷的研究现状与发展趋势．武汉理工大学学报．2002，24(2)， 12-15
[37]刘秋平．YNbO_4的合成制备及其介电性能的研究．北京交通大学．2007
[38]刘光华．稀土固体材料学．北京．机械工业出版社．1996，1-37
[39]周焕福，黄金亮．Y~(3+)取代Bi~(3+)的Bi_2O_3-ZnO-Nb_2O_5基陶瓷的结构与介电性．材料导报．2004， 18(11)：84-86
[40] Hakki B W and Coleman P D. A dielectric resonator method of measuring inductive capacitiesin the millimeter range. IEEE. Trans. MTT. 1960, 8:402-410
[41] Kim DW, Ko K H and Hong K S. Influence of Copper(Ⅱ) oxide additions to Zinc Niobatemicrowave ceramic sintering temperature and dielectric properties. J. Am. Ceram. Soc. 2001,84(6): 1286-1290
[42]黄永峰，李谦，黄金亮，龙永强．Bi_2O_3掺入对CLST微波介质陶瓷性能的影响．电子 元件与材料．2006年，第12期
[43] Solomon S, Santha N, Jawahar I N, et al. Tailoring the microwave dielectric properties ofBaRe_2Ti_4O_(12) and BaRe_2Ti_5O_(14) ceramics by compositional variations [J]. J Mater Sci: Materialsin Eletronics, 2000,11(8): 595-602
[44] Hu M Z, Zhou D X, Gu H S, et al. Influence of Bi_2O_3 and MnO_2 doping on microwaveproperties of [(Pb,Ca) La](Fe,Nb)O_3 dielectric ceramics[J]. Mater Sci Eng B, 2005,117(2):199-204
[45] John G. Thompson and Ray L. Withers. Modulated Structures in Oxidized CeriumNiobates. Journal of Solid State Chemistry 143:122-131 (1999)
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