CN102531599A - Sodium niobate/bismuth titanate lithium system leadless piezoelectric ceramic composition - Google Patents
Sodium niobate/bismuth titanate lithium system leadless piezoelectric ceramic composition Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 title claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims description 9
- 229910010293 ceramic material Inorganic materials 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 3
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- 229910003378 NaNbO3 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000028161 membrane depolarization Effects 0.000 description 2
- -1 molding Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052861 titanite Inorganic materials 0.000 description 1
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Abstract
一种新型的铌酸钠钛酸铋锂系无铅压电陶瓷组合物，其包含钙钛矿反铁电体NaNbO3和ABO3型化合物Bi0.5Li0.5TiO3，其通式用(1-x)NaNbO3-xBi0.5Li0.5TiO3来表示，式中0.025≤x≤0.25。该无铅压电陶瓷组合物还可以含有一种或多种氧化物，其通式为(1-x)NaNbO3-xBi0.5Li0.5TiO3((100-a)mol%)+MαOβ（amol%），MαOβ是一种或多种氧化物，其含量a占主要成分(1-x)NaNbO3-xBi0.5Li0.5TiO3的摩尔比为0-3%,M为+1至+6价且能与氧形成固态氧化物的元素，α和β分别表示相关氧化物中相应的元素M和氧的原子数。该体系压电陶瓷组合物的最优值d 33可达50pC/N以上，k p可达15%以上，居里温度高，热稳定性好，致密性好，工艺稳定，采用传统压电陶瓷制备技术制得。A novel sodium niobate bismuth titanate-based lead-free piezoelectric ceramic composition, which contains perovskite antiferroelectric NaNbO 3 and ABO 3 type compound Bi 0.5 Li 0.5 TiO 3 , whose general formula is (1- x) NaNbO 3 -xBi 0.5 Li 0.5 TiO 3 to represent, where 0.025≤x≤0.25. The lead-free piezoelectric ceramic composition may also contain one or more oxides whose general formula is (1-x)NaNbO 3 -xBi 0.5 Li 0.5 TiO 3 ((100-a)mol%)+M α O β (amol%), M α O β is one or more oxides, its content a accounts for the main component (1-x)NaNbO 3 -xBi 0.5 Li 0.5 TiO 3 molar ratio is 0-3%, M is Elements with a valence of +1 to +6 and capable of forming solid oxides with oxygen, α and β respectively represent the atomic numbers of the corresponding element M and oxygen in the relevant oxide. The optimal value d 33 of the piezoelectric ceramic composition of this system can reach more than 50pC/N, k p can reach more than 15%, the Curie temperature is high, the thermal stability is good, the compactness is good, the process is stable, and the traditional piezoelectric ceramics are used Prepared by technology.
Description
技术领域 technical field
本发明属于钙钛矿结构压电陶瓷领域，涉及一种新型的多元系铌酸盐无铅压电陶瓷组合物，特别是涉及一种铌酸钠钛酸铋锂系无铅压电陶瓷组合物。 The invention belongs to the field of perovskite structure piezoelectric ceramics, and relates to a novel multi-element niobate lead-free piezoelectric ceramic composition, in particular to a lead-free piezoelectric ceramic composition of sodium niobate bismuth titanate lithium series .
背景技术 Background technique
自二十世纪四十年代中期发现钛酸钡陶瓷的压电性，特别是具有优异压电性能和高居里温度的锆钛酸铅Pb(Ti,Zr)O3陶瓷开发成功后，结构特征为ABO3型的铅基钙钛矿压电陶瓷的研究开发非常活跃，压电陶瓷及压电陶瓷器件已广泛地应用于工业特别是信息产业领域。以锆钛酸铅(Pb(Ti,Zr)O3)为代表的铅基二元系和以锆钛酸铅(Pb(Ti,Zr)O3)为基、添加第三组元[如以铌镁酸铅(Pb(Mg1/3Nb2/3)O3)、锑锰酸铅Pb(Mn1/3Sb2/3)O3为代表]的铅基三元系压电陶瓷材料具有优良的压电铁电性能、高的居里温度。工业生产中应用的压电陶瓷绝大多数是该类钙钛矿铅基压电陶瓷。 Since the discovery of the piezoelectricity of barium titanate ceramics in the mid-1940s, especially the successful development of lead zirconate titanate Pb(Ti,Zr)O 3 ceramics with excellent piezoelectric properties and high Curie temperature, the structural characteristics are The research and development of ABO 3 type lead-based perovskite piezoelectric ceramics is very active. Piezoelectric ceramics and piezoelectric ceramic devices have been widely used in industry, especially in the field of information industry. Lead-based binary systems represented by lead zirconate titanate (Pb(Ti,Zr)O 3 ) and lead zirconate titanate (Pb(Ti,Zr)O 3 )-based, adding a third component [such as Lead-based ternary piezoelectric ceramic materials represented by lead magnesium niobate (Pb(Mg 1/3 Nb 2/3 )O 3 ) and lead antimonymanganate Pb(Mn 1/3 Sb 2/3 )O 3 It has excellent piezoelectric ferroelectric properties and high Curie temperature. The vast majority of piezoelectric ceramics used in industrial production are perovskite lead-based piezoelectric ceramics.
但是，铅基压电陶瓷材料中，PbO或Pb3O4的含量约占原料总量的70%。铅污染已成为人类公害之一。铅基压电陶瓷在生产、使用及废弃后处理过程中给人类及生态环境造成严重危害，不利于人类社会的可持续发展。近年来，开发不含铅的、性能优越的压电陶瓷体系受到世界各国特别是欧美、日本、韩国以及中国的日益重视。 However, in lead-based piezoelectric ceramic materials, the content of PbO or Pb 3 O 4 accounts for about 70% of the total amount of raw materials. Lead pollution has become one of human public hazards. Lead-based piezoelectric ceramics have caused serious harm to humans and the ecological environment in the process of production, use and disposal, and are not conducive to the sustainable development of human society. In recent years, the development of lead-free piezoelectric ceramic systems with superior performance has been paid more and more attention by countries all over the world, especially Europe, America, Japan, Korea and China.
目前广泛研究的无铅压电陶瓷体系有四类：铋层状结构无铅压电陶瓷、BaTiO3基无铅压电陶瓷、Bi0.5Na0.5TiO3基无铅压电陶瓷及K0.5Na0.5NbO3碱金属铌酸盐系无铅压电陶瓷。铋层状结构无铅压电陶瓷居里温度高，各向异性大，但压电活性极低；BaTiO3基压电陶瓷居里温度仅为120℃，室温附近存在铁电四方-铁电正交相界，电学性能的温度稳定性较差；Bi0.5Na0.5TiO3基无铅压电陶瓷具有压电性较强且易于改性提高压电性能的特点，但在210℃附近的第二相变致使退极化温度低于210℃，改性提高压电性能的同时往往伴随退极化温度的严重降低；K0.5Na0.5NbO3碱金属铌酸盐系无铅压电陶瓷通过引入ABO3型化合物或相似离子取代改性使铁电四方-铁电正交相变移向室温而提高压电性能，但室温铁电四方-铁电正交两相共存使电学性能的温度稳定性较差。 At present, there are four types of lead-free piezoelectric ceramic systems widely studied: bismuth layered structure lead-free piezoelectric ceramics, BaTiO 3- based lead-free piezoelectric ceramics, Bi 0.5 Na 0.5 TiO 3- based lead-free piezoelectric ceramics and K 0.5 Na 0.5 NbO 3 alkali metal niobate series lead-free piezoelectric ceramics. The lead-free piezoelectric ceramics with bismuth layer structure has high Curie temperature and large anisotropy, but the piezoelectric activity is extremely low; the Curie temperature of BaTiO 3 -based piezoelectric ceramics is only 120 ° C, and there are ferroelectric tetragonal-ferroelectric positive The temperature stability of electrical properties is poor; Bi 0.5 Na 0.5 TiO 3 -based lead-free piezoelectric ceramics have the characteristics of strong piezoelectricity and easy modification to improve piezoelectric performance, but the second temperature around 210 ° C The phase change causes the depolarization temperature to be lower than 210°C. The modification improves the piezoelectric performance and is often accompanied by a severe decrease in the depolarization temperature; K 0.5 Na 0.5 NbO 3 alkali metal niobate-based lead-free piezoelectric ceramics can Substitution modification of type 3 compounds or similar ions shifts the ferroelectric tetragonal-ferroelectric orthorhombic phase transition to room temperature and improves piezoelectric performance, but the coexistence of ferroelectric tetragonal-ferroelectric orthorhombic two phases at room temperature makes the temperature stability of electrical properties relatively low. Difference.
铌酸钠NaNbO3是正交结构钙钛矿反铁电体，被认为是最复杂的钙钛矿结构材料。随着温度的降低，依次发生顺电相-反铁电相-铁电相等六个结构相变(Phys. Rev. B, 76, 024110-1-8(2007))。在NaNbO3中引入ABO3型化合物，可以形成NaNbO3-CaTiO3(Phys. Rev. B 77, 052104 (2008)), NaNbO3-SrTiO3(Chem. Mater., 17, 1880-1886 (2005)), NaNbO3-BaSnO3(Solid State Sci. 6, 333-337 (2004)), NaNbO3-CaSnO3(J. Alloys Compd., 465, 222-226 (2008))等NaNbO3基体系，这些体系具有显著的弛豫特征而作为介电材料被深入研究，但不显示出压电性能。此外，在NaNbO3中引入铌酸盐铁电体如KNbO3(J. Am.Ceram. Soc., 82, 797–818 (1999))、LiNbO3(J. Appl. Phys., 48, 3014-3017 (1977))，可以得到压电体。除此之外，相对于上述四类无铅压电陶瓷，关于NaNbO3基无铅铁电压电陶瓷材料的研究极少。 Sodium niobate NaNbO3 is an orthorhombic structure perovskite antiferroelectric, which is considered to be the most complex perovskite structure material. As the temperature decreases, six structural phase transitions, paraelectric-antiferroelectric-ferroelectric, occur sequentially (Phys. Rev. B, 76, 024110-1-8(2007)). Introducing ABO 3 -type compounds into NaNbO 3 can form NaNbO 3 -CaTiO 3 (Phys. Rev. B 77, 052104 (2008)), NaNbO 3 -SrTiO 3 (Chem. Mater., 17, 1880-1886 (2005) ), NaNbO 3 -BaSnO 3 (Solid State Sci. 6, 333-337 (2004)), NaNbO 3 -CaSnO 3 (J. Alloys Compd., 465, 222-226 (2008)) and other NaNbO 3 -based systems, these The system is well-studied as a dielectric material due to its prominent relaxation features, but does not exhibit piezoelectric properties. In addition, niobate ferroelectrics such as KNbO 3 (J. Am.Ceram. Soc . , 82, 797–818 (1999)), LiNbO 3 (J. Appl. Phys., 48, 3014- 3017 (1977)), piezoelectric bodies can be obtained. Besides, compared with the above four types of lead-free piezoelectric ceramics, there are very few studies on NaNbO3 -based lead-free ferroelectric piezoelectric ceramic materials.
发明内容 Contents of the invention
本发明的目的在于提供一种铌酸钠钛酸铋锂系无铅压电陶瓷组合物，以解决现有技术上的上述问题。本发明所提供的组合物克服了已有的铅基压电陶瓷体系本身固有的缺陷，并改进了现有的无铅压电陶瓷性能。该类无铅压电陶瓷组合物采用传统陶瓷工艺制备，具有良好的压电性能，居里温度高，热稳定性好，致密性好，工艺稳定。 The purpose of the present invention is to provide a sodium niobate bismuth titanate lithium lead-free piezoelectric ceramic composition to solve the above-mentioned problems in the prior art. The composition provided by the invention overcomes the inherent defects of the existing lead-based piezoelectric ceramic system itself, and improves the performance of the existing lead-free piezoelectric ceramics. The lead-free piezoelectric ceramic composition is prepared by a traditional ceramic process and has good piezoelectric performance, high Curie temperature, good thermal stability, good compactness and stable process.
本发明提供的铌酸钠钛酸铋锂系无铅压电陶瓷组合物包含钙钛矿反铁电体NaNbO3和ABO3型化合物Bi0.5Li0.5TiO3。根据反铁电体NaNbO3及ABO3型化合物Bi0.5Li0.5TiO3本身固有的特点，本发明向反铁电体NaNbO3中引入Bi0.5Li0.5TiO3，固溶形成了一种新型的钙钛矿结构无铅压电陶瓷材料。 The sodium niobate bismuth titanate lead-free piezoelectric ceramic composition provided by the invention comprises perovskite antiferroelectric NaNbO 3 and ABO 3 type compound Bi 0.5 Li 0.5 TiO 3 . According to the inherent characteristics of antiferroelectric NaNbO 3 and ABO 3 type compound Bi 0.5 Li 0.5 TiO 3 , the present invention introduces Bi 0.5 Li 0.5 TiO 3 into antiferroelectric NaNbO 3 to form a new type of calcium Lead-free piezoceramic material with titanite structure.
本发明所提供的陶瓷组合物可以用通式(1-x)NaNbO3-xBi0.5Li0.5TiO3来表示，x表示相应元素所占的原子数，即原子百分比，式中0.025≤x≤0.25。 The ceramic composition provided by the present invention can be represented by the general formula (1-x) NaNbO 3 -xBi 0.5 Li 0.5 TiO 3 , x represents the number of atoms occupied by the corresponding element, that is, the atomic percentage, where 0.025≤x≤0.25 .
另外，本发明所述的铌酸钠钛酸铋锂系无铅压电陶瓷组合物中还可以进一步含有一种或多种氧化物，则组合物的通式为(1-x)NaNbO3-xBi0.5Li0.5TiO3((100-a)mol%)+MαOβ(amol%)，在式中MαOβ表示氧化物，α和β分别表示相关氧化物中相应的元素M和氧的原子数，amol%为该氧化物占组合物总体的摩尔比，其中0≤a≤3。M为+1至+6价且能与氧形成固态氧化物的元素，其包括但不限于至少一种选自Na、K、Li、Ni、Zn、Cr、Co、Nb、Ta、Al、Cu、Fe、Ce、Pr、Nd、Sm、Gd、Dy、Er、Yb、In、Y、Sc、La、Ho、Lu、Sn、Sb、Mn、Ca、Ba、Sr、Mg、Si、Bi或Ag的元素。优选M为Mn。 In addition, the sodium niobate bismuth titanate lithium lead-free piezoelectric ceramic composition described in the present invention may further contain one or more oxides, and the general formula of the composition is (1-x)NaNbO 3 - xBi 0.5 Li 0.5 TiO 3 ((100-a)mol%)+M α O β (amol%), where M α O β represents the oxide, and α and β represent the corresponding elements M and The number of atoms of oxygen, amol% is the molar ratio of the oxide to the overall composition, where 0≤a≤3. M is an element with a valence of +1 to +6 and can form a solid oxide with oxygen, including but not limited to at least one selected from Na, K, Li, Ni, Zn, Cr, Co, Nb, Ta, Al, Cu , Fe, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, In, Y, Sc, La, Ho, Lu, Sn, Sb, Mn, Ca, Ba, Sr, Mg, Si, Bi or Ag Elements. Preferably M is Mn.
本发明提出的压电陶瓷材料还可以由前面通式表示的基料添加氧化物(即基料+掺杂物)组成，使一些性能优化。可以用通式表示为(1-x)NaNbO3-xBi0.5Li0.5TiO3((100-a)mol%）+MαOβ(amol%)，在式中MαOβ表示掺杂物，掺杂物所占的比重为0-3mol％。MαOβ 是一种或多种掺杂氧化物，M为+1至+6价且能与氧形成固态氧化物的元素，如Na、K、Li、Ni、Zn、Cr、Co、Nb、Ta、Al、Cu、Fe、Ce、Pr、Nd、Sm、Gd、Dy、Er、Yb、In、Y、Sc、La、Ho、Lu、Sn、Sb、Mn、Ca、Ba、Sr、Mg、Si、Bi、Ag等，α和β分别表示相关氧化物中相应的元素M和氧的原子数。 The piezoelectric ceramic material proposed by the present invention can also be composed of base material represented by the above general formula plus oxide (ie, base material + dopant), so as to optimize some properties. It can be expressed by the general formula as (1-x)NaNbO 3 -xBi 0.5 Li 0.5 TiO 3 ((100-a)mol%)+M α O β (amol%), where M α O β represents the dopant , the proportion of dopant is 0-3mol%. M α O β is one or more doped oxides, M is an element with a valence of +1 to +6 and can form a solid oxide with oxygen, such as Na, K, Li, Ni, Zn, Cr, Co, Nb , Ta, Al, Cu, Fe, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, In, Y, Sc, La, Ho, Lu, Sn, Sb, Mn, Ca, Ba, Sr, Mg , Si, Bi, Ag, etc., α and β represent the atomic numbers of the corresponding elements M and oxygen in the relevant oxides, respectively.
本发明所述的铌酸钠钛酸铋锂系无铅压电陶瓷组合物具有优良的压电铁电性能，经材料性能测试，压电常数d 33可达50pC/N以上，k p可达15%以上，居里温度高，热稳定性好。本发明提供的组合物的优点是：压电性能优良；居里温度高，热稳定性好；制备工艺稳定，采用传统压电陶瓷制备技术获得；烧结温度低，约为1200℃。通过进一步含有氧化物，可以调制该无铅压电陶瓷组合物的一些性能参数。 The sodium niobate bismuth titanate lithium lead-free piezoelectric ceramic composition of the present invention has excellent piezoelectric ferroelectric properties, and through material performance tests, the piezoelectric constant d33 can reach more than 50pC/N, and kp can reach More than 15%, the Curie temperature is high, and the thermal stability is good. The composition provided by the invention has the advantages of excellent piezoelectric performance; high Curie temperature and good thermal stability; stable preparation process obtained by adopting traditional piezoelectric ceramic preparation technology; low sintering temperature of about 1200°C. By further containing oxides, some performance parameters of the lead-free piezoelectric ceramic composition can be adjusted.
附图说明 Description of drawings
图1是本发明测得的0.925NaNbO3-0.075Bi0.5Li0.5TiO3无铅压电陶瓷在室温下的电滞回线。 Fig. 1 is the hysteresis loop at room temperature of the 0.925NaNbO 3 -0.075Bi 0.5 Li 0.5 TiO 3 lead-free piezoelectric ceramics measured in the present invention.
图2是本发明测得的0.925NaNbO3-0.075Bi0.5Li0.5TiO3的压电常数d33及机电耦合系数kp与温度T的关系。 Fig. 2 is the relationship between the piezoelectric constant d 33 and the electromechanical coupling coefficient k p of 0.925NaNbO 3 -0.075Bi 0.5 Li 0.5 TiO 3 measured by the present invention and the temperature T.
具体实施方式 Detailed ways
以下将通过实施例对本发明进行详细描述，这些实施例只是出于示例性说明的目的，而并非用于限定本发明。 The present invention will be described in detail through examples below, and these examples are only for the purpose of illustration and description, and are not intended to limit the present invention.
制备本发明所述通式为(1-x)NaNbO3-xBi0.5Li0.5TiO3的无铅压电陶瓷可以采用工业纯、化学纯或分析纯的Na2CO3、Li2CO3、Bi2O3、TiO2、Nb2O5为原料，按照常规制备方法制得。例如，其中的一种方法是根据通式的化学计量比称量原料，经充分球磨混匀后，装入氧化铝坩埚内，在800-900℃进行预烧，保温时间为6小时，再经球磨磨细、充分混合、加粘结剂、成型、排塑，最后在1200℃下烧结2-6小时。烧结后的陶瓷片被上银电极，在60℃的硅油中，在3-6kV/mm的电压下极化30-40分钟。 The preparation of lead-free piezoelectric ceramics with the general formula (1-x)NaNbO 3 -xBi 0.5 Li 0.5 TiO 3 according to the present invention can use industrially pure, chemically pure or analytically pure Na 2 CO 3 , Li 2 CO 3 , Bi 2 O 3 , TiO 2 , and Nb 2 O 5 are used as raw materials and prepared according to conventional preparation methods. For example, one of the methods is to weigh the raw materials according to the stoichiometric ratio of the general formula, put them into an alumina crucible after being fully ball-milled and mixed, and pre-fire at 800-900 ° C for 6 hours, and then Ball milling, fully mixing, adding binder, molding, plastic discharge, and finally sintering at 1200°C for 2-6 hours. The sintered ceramic sheet is covered with a silver electrode, and polarized at a voltage of 3-6kV/mm for 30-40 minutes in silicone oil at 60°C.
制备本发明所述通式为(1-x)NaNbO3-xBi0.5Li0.5TiO3（（100-a）mol%）+MαOβ（amol%）的无铅压电陶瓷的一种方法是，可以采用工业纯、化学纯或分析纯的Na2CO3、Li2CO3、Bi2O3、TiO2、Nb2O5为原料，按其通式的化学计量比称量原料，经充分球磨混匀后，装入氧化铝坩埚内，在800-900℃进行预烧，保温时间为6小时。预烧合成的粉料中加入适量的工业纯、化学纯或分析纯MαOβ改性添加剂，再经球磨磨细、充分混合、加粘结剂、成型、排塑，最后在1200℃下烧结2-6小时。烧结后的陶瓷片被上银电极，在60℃的硅油中，在3-6kV/mm的电压下极化30-40分钟。 A method for preparing lead-free piezoelectric ceramics with the general formula (1-x)NaNbO 3 -xBi 0.5 Li 0.5 TiO 3 ((100-a) mol%)+M α O β (amol%) of the present invention Yes, industrially pure, chemically pure or analytically pure Na 2 CO 3 , Li 2 CO 3 , Bi 2 O 3 , TiO 2 , Nb 2 O 5 can be used as raw materials, and the raw materials can be weighed according to the stoichiometric ratio of their general formula, After fully ball-milling and mixing, put it into an alumina crucible, and pre-fire it at 800-900°C, and the holding time is 6 hours. Add an appropriate amount of industrially pure, chemically pure or analytically pure M α O β modifying additives to the powder synthesized by pre-sintering, and then go through ball milling, fully mixing, adding binder, molding, plastic discharge, and finally at 1200 ° C Sinter for 2-6 hours. The sintered ceramic sheet is covered with a silver electrode, and polarized at a voltage of 3-6kV/mm for 30-40 minutes in silicone oil at 60°C.
the
按照上述方法制备的无铅压电陶瓷的配方和性能指标如下： The formula and performance index of the lead-free piezoelectric ceramic prepared according to the above-mentioned method are as follows:
实施例1： Example 1:
配方：0.95NaNbO3-0.05Bi0.5Li0.5TiO3 Formula: 0.95NaNbO 3 -0.05Bi 0.5 Li 0.5 TiO 3
性能： performance:
d 33(pC/N) ε r k p(%) tanδ(%) d 33 (pC/N) ε r k p (%) tanδ(%)
54 290 17.5 5.80 54 290 17.5 5.80
实施例2： Example 2:
配方：0.925NaNbO3-0.075Bi0.5Li0.5TiO3 Formula: 0.925NaNbO 3 -0.075Bi 0.5 Li 0.5 TiO 3
性能： performance:
d 33(pC/N) ε r k p(%) tanδ(%) d 33 (pC/N) ε r k p (%) tanδ(%)
59 338 17.3 3.50 59 338 17.3 3.50
实施例3： Example 3:
配方：0.90NaNbO3-0.10Bi0.5Li0.5TiO3 Formula: 0.90NaNbO 3 -0.10Bi 0.5 Li 0.5 TiO 3
性能： performance:
d 33(pC/N) ε r k p(%) tanδ(%) d 33 (pC/N) ε r k p (%) tanδ(%)
46 443 11.4 1.50 46 443 11.4 1.50
实施例4： Example 4:
配方：0.90NaNbO3-0.10Bi0.5Li0.5TiO3 (99.5mol%)+MnO2(0.5mol%) Formula: 0.90NaNbO 3 -0.10Bi 0.5 Li 0.5 TiO 3 (99.5mol%)+MnO 2 (0.5mol%)
性能： performance:
d 33(pC/N) ε r k p(%) tanδ(%) d 33 (pC/N) ε r k p (%) tanδ(%)
60 292 18.0 4.9 60 292 18.0 4.9
实施例5： Example 5:
配方：0.90NaNbO3-0.10Bi0.5Li0.5TiO3 (99mol%)+MnO2(1mol%) Formula: 0.90NaNbO 3 -0.10Bi 0.5 Li 0.5 TiO 3 (99mol%)+MnO 2 (1mol%)
性能： performance:
d 33(pC/N) ε r k p(%) tanδ(%) d 33 (pC/N) ε r k p (%) tanδ(%)
59 287 17.3 2.60 59 287 17.3 2.60
实施例6： Embodiment 6:
配方：0.90NaNbO3-0.10Bi0.5Li0.5TiO3 (98.5mol%)+MnO2(1.5mol%) Formula: 0.90NaNbO 3 -0.10Bi 0.5 Li 0.5 TiO 3 (98.5mol%)+MnO 2 (1.5mol%)
性能： performance:
d 33(pC/N) ε r k p(%) tanδ(%) d 33 (pC/N) ε r k p (%) tanδ(%)
58 36 17.2 2.36 58 36 17.2 2.36
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108585851A (en) * | 2018-07-10 | 2018-09-28 | 合肥工业大学 | A kind of unleaded no potassium high-power piezoelectric ceramic of sodium niobate base and preparation method thereof |
| CN108865108A (en) * | 2018-08-03 | 2018-11-23 | 广东工业大学 | A kind of niobates off-color material and preparation method thereof |
| CN109503153A (en) * | 2018-12-14 | 2019-03-22 | 陕西科技大学 | A kind of high energy-storage property media ceramic, preparation method and applications |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823878A (en) * | 2010-04-23 | 2010-09-08 | 四川师范大学 | Sodium potassium hafnium zirconium niobate calcium titanate lead-free piezoelectric ceramic composition |
| CN102234195A (en) * | 2010-04-23 | 2011-11-09 | 四川师范大学 | Potassium-sodium niobate and sodium lithium bismuth titanate-system lead-free piezoelectric ceramic composition |
-
2011
- 2011-12-22 CN CN2011104353263A patent/CN102531599A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823878A (en) * | 2010-04-23 | 2010-09-08 | 四川师范大学 | Sodium potassium hafnium zirconium niobate calcium titanate lead-free piezoelectric ceramic composition |
| CN102234195A (en) * | 2010-04-23 | 2011-11-09 | 四川师范大学 | Potassium-sodium niobate and sodium lithium bismuth titanate-system lead-free piezoelectric ceramic composition |
Non-Patent Citations (4)
| Title |
|---|
| 《J Mater Sci: Mater Electron》 20110615 Dunmin Lin et al. Structure and piezoelectric properties of K0.5Na0.5NbO3-Bi0.5Li0.5TiO3 lead-free ceramics 摘要，第501页右栏第2段，第502页左栏第2段 1-3 第23卷, * |
| DUNMIN LIN ET AL.: "Structure and piezoelectric properties of K0.5Na0.5NbO3–Bi0.5Li0.5TiO3 lead-free ceramics", 《J MATER SCI: MATER ELECTRON》, vol. 23, 15 June 2011 (2011-06-15) * |
| S. I. RAEVSKAYA ET AL.: "Structural and Dielectric Studies of NaNbO3-A0.5Bi0.5TiO3 (A-Li,Na,K) Solid Solutions", 《FERROELECTRICS》, vol. 399, no. 1, 23 June 2010 (2010-06-23) * |
| 罗泳文等: "铌酸钠无铅陶瓷的制备和性能研究", 《功能材料》, vol. 42, no. 7, 20 July 2011 (2011-07-20) * |
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| CN108585851A (en) * | 2018-07-10 | 2018-09-28 | 合肥工业大学 | A kind of unleaded no potassium high-power piezoelectric ceramic of sodium niobate base and preparation method thereof |
| CN108585851B (en) * | 2018-07-10 | 2021-01-05 | 合肥工业大学 | Sodium niobate-based lead-free potassium-free high-power piezoelectric ceramic and preparation method thereof |
| CN108865108A (en) * | 2018-08-03 | 2018-11-23 | 广东工业大学 | A kind of niobates off-color material and preparation method thereof |
| CN108865108B (en) * | 2018-08-03 | 2021-04-16 | 广东工业大学 | A kind of niobate color changing material and preparation method thereof |
| CN109503153A (en) * | 2018-12-14 | 2019-03-22 | 陕西科技大学 | A kind of high energy-storage property media ceramic, preparation method and applications |
| CN110668816A (en) * | 2019-10-16 | 2020-01-10 | 电子科技大学 | Lead-free energy storage dielectric ceramic material with tungsten bronze structure and preparation method thereof |
| CN110668816B (en) * | 2019-10-16 | 2021-11-02 | 电子科技大学 | A kind of tungsten bronze structure lead-free energy storage medium ceramic material and preparation method thereof |
| CN111153697A (en) * | 2020-01-14 | 2020-05-15 | 西安工业大学 | Wide-stability narrow-band potassium sodium niobate-based ferroelectric ceramic material and preparation method thereof |
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