CN1260171C - Bismuth sodium titanate barium titanate strontium titanate calcium titanate based lead-free piezoelectric ceramics - Google Patents
Bismuth sodium titanate barium titanate strontium titanate calcium titanate based lead-free piezoelectric ceramics Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- 229910002113 barium titanate Inorganic materials 0.000 title claims description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims description 3
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 title claims 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 title claims 2
- 239000011734 sodium Substances 0.000 claims abstract description 47
- 239000011575 calcium Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 10
- -1 compound ion Chemical class 0.000 claims description 6
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 17
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- MUSRXJYSDKILRA-UHFFFAOYSA-N [Ca].[Sr].[Ba].[Na].[Bi] Chemical compound [Ca].[Sr].[Ba].[Na].[Bi] MUSRXJYSDKILRA-UHFFFAOYSA-N 0.000 abstract 1
- 239000002019 doping agent Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910020215 Pb(Mg1/3Nb2/3)O3PbTiO3 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 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 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 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
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
钛酸铋钠钡锶钙系无铅压电陶瓷，涉及一种新型的多元系无铅压电陶瓷组合物，属于钙钛矿结构环境协调性压电陶瓷领域。本发明提出的无铅压电陶瓷可以用通式(1-z)Bi(1-w)NawTiO3+z(Ba1-x-ySrxCay)TiO3+aMαOβ(wt%)来表示，式中0＜x＜1，0＜y＜1，0＜z＜1，0＜(x+y)＜1，0.3≤w≤0.7，MαOβ是一种或多种掺杂氧化物，其含量a占主要成分(1-z)Bi(1-w)NawTiO3+z(Ba1-x-ySrxCay)TiO3的重量比为0-10%，M为+1-+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。该体系压电陶瓷组合物d33可达160pC/N以上，kp可达30.0%以上，其工艺稳定，可采用传统压电陶瓷制备技术和工业用原材料获得，具有实用性。The invention relates to a lead-free piezoelectric ceramic of bismuth sodium barium strontium calcium titanate series, relates to a novel multi-element lead-free piezoelectric ceramic composition, and belongs to the field of perovskite structure-environment coordination piezoelectric ceramics. The lead-free piezoelectric ceramics proposed by the present invention can use the general formula (1-z)Bi (1-w) Na w TiO 3 +z(Ba 1-xy Sr x Ca y )TiO 3 +aM α O β (wt% ), where 0<x<1, 0<y<1, 0<z<1, 0<(x+y)<1, 0.3≤w≤0.7, M α O β is one or more Doped oxide, its content a accounts for 0-10% by weight of the main component (1-z)Bi (1-w) Na w TiO 3 +z(Ba 1-xy Sr x Ca y )TiO 3 , M Elements that are +1-+6 valent and can form solid oxides 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, etc., α and β respectively represent the corresponding elements in the related oxides M and the atomic number of oxygen. The piezoelectric ceramic composition d 33 of the system can reach more than 160pC/N, and the k p can reach more than 30.0%.
Description
一、技术领域1. Technical field
本发明涉及一种新型的多元系无铅压电陶瓷组合物，属于钙钛矿结构环境协调性压电陶瓷领域。The invention relates to a novel multi-component lead-free piezoelectric ceramic composition, which belongs to the field of piezoelectric ceramics with perovskite structure and environment coordination.
二、背景技术2. Background technology
自二十世纪四十年代中期发现钛酸钡陶瓷的压电性后，结构特征为AB O3型的压电陶瓷的研究开发非常活跃，压电陶瓷及制作的元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，A位为Pb；B位为Ti，Zr和以铌镁酸铅-钛酸铅[Pb(Mg1/3Nb2/3)O3-PbTiO3]为基料，添加第三组元，如以铌镁酸铅(Pb(Mg1/3Nb2/3)O3)为代表，A位为Pb，B位为Mg1/3Nb2/3和Ti的铅基三元系压电陶瓷材料都具有优良的压电铁电性能和高的居里温度。工业生产中应用的压电陶瓷绝大多数是该类铅基压电陶瓷。Since the discovery of the piezoelectricity of barium titanate ceramics in the mid-1940s, the research and development of piezoelectric ceramics with structural characteristics of the AB O 3 type has been very active, and piezoelectric ceramics and their components have been widely used in industry. Especially in the field of information industry. Lead-based binary system represented by lead zirconate titanate (Pb(Ti, Zr)O 3 ), the A site is Pb; the B site is Ti, Zr and lead magnesium niobate-lead titanate [Pb(Mg 1 /3 Nb 2/3 )O 3 -PbTiO 3 ] as the base material, add the third component, such as lead magnesium niobate (Pb(Mg 1/3 Nb 2/3 )O 3 ) as the representative, the A position is Pb, lead-based ternary piezoelectric ceramic materials with B sites of Mg 1/3 Nb 2/3 and Ti all have excellent piezoelectric ferroelectric properties and high Curie temperature. The vast majority of piezoelectric ceramics used in industrial production are lead-based piezoelectric ceramics.
但是，在铅基压电陶瓷材料中的PbO或Pb3O4含量约占原料总量的70％。PbO或Pb3O4在高温下易挥发，从而使铅基压电陶瓷在生产、使用及废弃后的处理过程中给人类及生态环境造成严重污染和危害。近年来，寻找不含铅的、性能优越的压电陶瓷体系受到世界各国的日益重视。However, the content of PbO or Pb 3 O 4 in lead-based piezoelectric ceramic materials accounts for about 70% of the total amount of raw materials. PbO or Pb 3 O 4 is volatile at high temperature, which causes serious pollution and harm to human beings and the ecological environment during the production, use and disposal of lead-based piezoelectric ceramics. In recent years, the search for lead-free piezoelectric ceramic systems with superior performance has been paid more and more attention by countries all over the world.
目前常见的无铅压电陶瓷体系有四类：BaTiO3基无铅压电陶瓷、铋层状结构无铅压电陶瓷、碱金属铌酸盐无铅压电陶瓷及Bi0.5Na0.5TiO3基无铅压电陶瓷。以上四类无铅压电陶瓷的特点是：BaTiO3基压电陶瓷居里温度仅为120℃，压电性能中等：铋层状结构无铅压电陶瓷的居里温度高，但压电活性低；碱金属铌酸盐无铅压电陶瓷则难以烧结成致密的陶瓷；Bi0.5Na0.5TiO3基无铅压电陶瓷具有居里温度高、易添加其它组元改性以提高压电性能等特点成为了非铅基压电陶瓷的研究热点。At present, there are four types of common lead-free piezoelectric ceramic systems: BaTiO 3 -based lead-free piezoelectric ceramics, bismuth layered structure lead-free piezoelectric ceramics, alkali metal niobate lead-free piezoelectric ceramics and Bi 0.5 Na 0.5 TiO 3 -based Lead-free piezoelectric ceramics. The characteristics of the above four types of lead-free piezoelectric ceramics are: the Curie temperature of BaTiO3-based piezoelectric ceramics is only 120 ° C, and the piezoelectric performance is medium; the Curie temperature of lead-free piezoelectric ceramics with bismuth layer structure is high, but the piezoelectric activity is low. Alkali metal niobate lead-free piezoelectric ceramics are difficult to sinter into dense ceramics; Bi 0.5 Na 0.5 TiO 3 -based lead-free piezoelectric ceramics have high Curie temperature, easy to add other components to modify to improve piezoelectric performance, etc. The characteristics have become a research hotspot of non-lead-based piezoelectric ceramics.
Bi0.5Na0.5TiO3是A位由复合离子Bi0.5Na0.5构成的ABO3钙钛矿型铁电体，A位复合离子Bi0.5Na0.5由Bi3+(A1位)和Na+(A2位)构成。单纯的Bi0.5Na0.5TiO3陶瓷矫顽场极大(73Kv/cm)，极化困难，难以实用化，必须对Bi0.5Na0.5TiO3进行改性以获得矫顽场低，压电铁电性能佳的无铅压电陶瓷体系。目前常见的对Bi0.5Na0.5TiO3添加其它组元进行改性的方法有单纯地以+2价碱土金属离子部分取代A位离子Bi0.5Na0.5或单纯地+1价的碱金属离子部分取代A2位的Na+。文献1(JAPANESE JOURNAL OF APPLIED PHYSICS，Vol30，9B，1991，9，p2236-2239)、文献2(无机材料学报，Vol 15，No5，2000，12)给出了组成式为(1-x)Bi0.5Na0.5TiO3-xBaTiO3的无铅压电陶瓷体系，d33＝125pC/N，kp＝29％；文献3(phys.stat.sol.(a)157，499(1996))给出了组成式为Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3的无铅压电陶瓷体系，d33＝96pC/N，kp＝21％；文献4(Ferroelectrics.1997，Vol 196，p 175-178)和文献5(Key Engineering Materials Vols，157-158(1999)p.57-64)分别给出了组成式为Bi0.5Na0.5TiO3-1/2(Bi2O3·Sc2O3)、Bi0.5Na0.5TiO3-NaNbO3的无铅压电陶瓷体系，d33＝71-92pC/N，kp约为15％；文献6(Ferroelectrics.1995，Vol 169，p 317-325)和7(Ferroelectrics.1990，Vol 106，p 375-380)给出了组成式为(Bi1/2Na1/2)1-x(Sr1/2Ca1/2)xTiO3、(Bi1/2Na1/2)1-x(SraPbbCac)xTiO3无铅压电陶瓷体系，d33＝82pC/N，kp＝12-20.3％。专利CN85100513、JP2001-48642提供了组成式为(1-x)Bi0.5Na0.5TiO3-xBaTiO3的压电陶瓷组合物，kp＝20.2％，ε33/ε0＝290，d33＝159pC/N；专利JP11-217262、JP2000-22235提供了组成式为[Bi0.5(Na1-xKx)0.5]TiO3的压电陶瓷组合物，kp＝21.1％，ε33/ε0＝611。专利DE19530592C2给出了组成式为Bi0.5Na0.5TiO3-BaTiO3-CaTiO3的压电陶瓷组合物，该组合物具有厚度与径向机电耦合系数各向异性大的特点，kp＝16％；专利JP2000-44335给出了组成式为[Bi0.5(Na1-xLix)0.5]TiO3的压电陶瓷组合物，kp＝23.4％，ε33/ε0＝432。Bi 0.5 Na 0.5 TiO 3 is an ABO 3 perovskite ferroelectric composed of composite ions Bi 0.5 Na 0.5 at the A site, and the composite ion Bi 0.5 Na 0.5 at the A site is composed of Bi 3+ (A1 site) and Na + (A2 site )constitute. The pure Bi 0.5 Na 0.5 TiO 3 ceramic has a very large coercive field (73Kv/cm), difficult to polarize, and is difficult to be practical. It is necessary to modify Bi 0.5 Na 0.5 TiO 3 to obtain a low coercive field, piezoelectric ferroelectric Lead-free piezoelectric ceramic system with excellent performance. Currently common methods for modifying Bi 0.5 Na 0.5 TiO 3 by adding other components include simply substituting the A-site ion Bi 0.5 Na 0.5 with +2-valent alkaline earth metal ions or simply substituting +1-valent alkali metal ions Na + at A2 position. Document 1 (JAPANESE JOURNAL OF APPLIED PHYSICS, Vol30, 9B, 1991, 9, p2236-2239), Document 2 (Journal of Inorganic Materials, Vol 15, No5, 2000, 12) give the composition formula as (1-x) Bi 0.5 Na 0.5 TiO 3 -xBaTiO 3 lead-free piezoelectric ceramic system, d 33 =125pC/N, k p =29%; Document 3 (phys.stat.sol.(a)157,499(1996)) gives A lead-free piezoelectric ceramic system with the composition formula Bi 0.5 Na 0.5 TiO 3 -Bi 0.5 K 0.5 TiO 3 was established, d 33 =96pC/N, k p =21%; Document 4 (Ferroelectrics.1997, Vol 196, p 175 -178) and literature 5 (Key Engineering Materials Vols, 157-158 (1999) p.57-64) respectively give the composition formula as Bi 0.5 Na 0.5 TiO 3 -1/2(Bi 2 O 3 Sc 2 O 3 ), Bi 0.5 Na 0.5 TiO 3 -NaNbO 3 lead-free piezoelectric ceramic system, d 33 =71-92pC/N, k p is about 15%; Document 6 (Ferroelectrics.1995, Vol 169, p 317-325 ) and 7 (Ferroelectrics.1990, Vol 106, p 375-380) give the composition formula as (Bi 1/2 Na 1/2 ) 1-x (Sr 1/2 Ca 1/2 ) x TiO 3 , ( Bi 1/2 Na 1/2 ) 1-x (Sr a Pb b Ca c ) x TiO 3 lead-free piezoelectric ceramic system, d 33 =82pC/N, k p =12-20.3%. Patents CN85100513 and JP2001-48642 provide piezoelectric ceramic compositions with composition formula (1-x)Bi 0.5 Na 0.5 TiO 3 -xBaTiO 3 , k p =20.2%, ε 33 /ε 0 =290, d 33 =159pC /N; Patents JP11-217262 and JP2000-22235 provide a piezoelectric ceramic composition whose composition formula is [Bi 0.5 (Na 1-x K x ) 0.5 ]TiO 3 , k p =21.1%, ε 33 /ε 0 = 611. Patent DE19530592C2 provides a piezoelectric ceramic composition with a composition formula of Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 -CaTiO 3 , which has the characteristics of large anisotropy in thickness and radial electromechanical coupling coefficient, k p = 16% ; Patent JP2000-44335 provides a piezoelectric ceramic composition with the composition formula [Bi 0.5 (Na 1-x Li x ) 0.5 ]TiO 3 , k p =23.4%, ε 33 /ε 0 =432.
三、发明内容3. Contents of the invention
本发明的目的就是为了克服已有的铅基压电陶瓷体系本身固有的缺陷，改进现有BaTiO3基无铅电池性能，提出了一类新型的由多元系无铅材料组成无铅压电陶瓷。该压电陶瓷采用传统陶瓷工艺制备，工艺稳定性好，具有优良的压电铁电性能，已接近于铅基陶瓷的产品性能，具有实用性。The purpose of the present invention is to overcome the inherent defects of the existing lead-based piezoelectric ceramic system itself, improve the performance of the existing BaTiO 3 -based lead-free battery, and propose a new type of lead-free piezoelectric ceramic composed of multi-element lead-free materials. . The piezoelectric ceramic is prepared by a traditional ceramic process, has good process stability, has excellent piezoelectric ferroelectric properties, is close to the product performance of lead-based ceramics, and is practical.
为实现本发明的目的，本发明针对ABO3结构的钙钛矿型压电体系(Bi0.5Na0.5)TiO3，提出了一类A位复合离子Bi0.5Na0.5部分被碱土金属离子Ba、Sr、Ca组成的复合离子Ba1-x-ySrxCay取代所形成的新型无铅压电陶瓷材料，可以用通式(1-z)Bi(1-w)NawTiO3+z(Ba1-x-ySrxCay)TiO3来表示，式中的x、y、z和w表示复合离子中相应元素材料在各组元中所占的原子数(即原子百分比)。A位上的所有元素的原子数总和应为1，式中x、y、z和w的数值为：0＜x＜1，0＜y＜1，0＜z＜1，0＜(x+y)＜1，0.3≤w≤0.7。In order to achieve the purpose of the present invention, the present invention proposes a kind of A-site compound ion Bi 0.5 Na 0.5 partially covered by alkaline earth metal ions Ba, Sr for the perovskite piezoelectric system (Bi 0.5 Na 0.5 )TiO 3 with ABO 3 structure , Ca composed of composite ions Ba 1-xy Sr x Ca y to replace the formed new lead-free piezoelectric ceramic material, the general formula (1-z)Bi (1-w) Na w TiO 3 +z(Ba 1 -xy Sr x Ca y ) TiO 3 , where x, y, z and w represent the number of atoms (that is, the atomic percentage) of the corresponding element materials in each component in the compound ion. The sum of the atomic numbers of all elements on the A position should be 1, and the values of x, y, z and w in the formula are: 0<x<1, 0<y<1, 0<z<1, 0<(x+ y)<1, 0.3≤w≤0.7.
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其他金属作为掺杂物，即基料+掺杂物组成，使其性能更加优化。可以用通式表示为：(1-z)Bi(1-w)NawTiO3+z(Ba1-x-ySrxCay)TiO3+MαOβ(wt％)，在通式中MαOβ表示掺杂物。掺杂物所占的比例为0-10wt％；基料所占的比例为90-100wt％。MαOβ是一种或多种掺杂氧化物，M代表这类+1-+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 the base material represented by the general formula above and other metals as dopants, that is, base material + dopant, so as to optimize its performance. It can be expressed as: (1-z)Bi (1-w) Na w TiO 3 +z(Ba 1-xy Sr x Ca y )TiO 3 +M α O β (wt%), in the general formula M α O β represents a dopant. The proportion of dopant is 0-10wt%; the proportion of base material is 90-100wt%. M α O β is one or more doped oxides, M represents this type of +1-+6 elements that can form solid oxides 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, etc.; α and β represent the atomic numbers of the corresponding elements M and oxygen in the relevant oxides, respectively.
本发明的多元系无铅压电陶瓷，具有优良的压电铁电性能，经材料性能检测，该体系压电陶瓷的压电常数d33可达160pC/N以上，耦合系数kp可达30.0％以上。本发明的优点是：无铅压电陶瓷性能优良，已具有工业产品的性能水平；其工艺稳定，可采用传统压电陶瓷制备技术和工业用原材料获得，烧结温度约为1175-1225℃，较铅基压电陶瓷低约50-100℃，具有实用性。The multi-component lead-free piezoelectric ceramics of the present invention have excellent piezoelectric ferroelectric properties, and the piezoelectric constant d 33 of the piezoelectric ceramics of the system can reach more than 160 pC/N, and the coupling coefficient k p can reach 30.0 %above. The advantages of the present invention are: lead-free piezoelectric ceramics have excellent performance and have the performance level of industrial products; the process is stable and can be obtained by using traditional piezoelectric ceramic preparation technology and industrial raw materials, and the sintering temperature is about 1175-1225 ° C, which is relatively high Lead-based piezoelectric ceramics have a low temperature of about 50-100°C and are practical.
四、具体实施方式4. Specific implementation
制备本发明的无铅压电陶瓷可以采用工业纯或化学纯的Bi2O3、Na2CO3、BaCO3、SrCO3、CaCO3、TiO2、MαOβ为原料，可以根据需要来选择相关金属氧化物作为掺杂物MαOβ。具体的制备方法是：按通式(1-z)Bi(1-w)NawTiO3+z(Ba1-x-ySrxCay)TiO3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2-6小时；预烧合成的粉料中加入awt％改性添加剂MαOβ，再经球磨磨细、充分混合、加粘结剂、成型、排塑，最后在1075-1225℃下烧结2-3小时。烧结后的陶瓷片被上银电极，在60-120℃的硅油中，在3-4kV/mm的电压下极化10-20分钟。The preparation of lead-free piezoelectric ceramics of the present invention can use industrially pure or chemically pure Bi 2 O 3 , Na 2 CO 3 , BaCO 3 , SrCO 3 , CaCO 3 , TiO 2 , and M α O β as raw materials, which can be selected according to needs Related metal oxides as dopants M α O β . The specific preparation method is: weighing the raw materials according to the stoichiometric ratio of the general formula (1-z)Bi (1-w) Na w TiO 3 +z(Ba 1-xy Sr x Ca y )TiO 3 After uniformity, put it into an alumina crucible, pre-fire at 800-900°C, and hold for 2-6 hours; add awt% modified additive M α O β to the pre-fired synthetic powder, and then grind it finely by ball milling , Mix well, add binder, shape, discharge plastic, and finally sinter at 1075-1225°C for 2-3 hours. The sintered ceramic sheet is covered with a silver electrode, and polarized at a voltage of 3-4kV/mm for 10-20 minutes in silicone oil at 60-120°C.
制备体系(1-z)Bi(1-w)NawTiO3+z(Ba1-x-ySrxCay)TiO3(92-100wt％)或添加掺杂物MαOβ(0-8wt％)的无铅压电陶瓷的配方及性能指标如下：Preparation system (1-z)Bi (1-w) Na w TiO 3 +z(Ba 1-xy Sr x Ca y )TiO 3 (92-100wt%) or adding dopant M α O β (0-8wt %) of the lead-free piezoelectric ceramic formulation and performance indicators are as follows:
实施例1：Example 1:
配方：formula:
0.915Bi0.5Na0.5TiO3+0.085(Ba0.7Sr0.18Ca0.12)TiO3 0.915Bi 0.5 Na 0.5 TiO 3 +0.085(Ba 0.7 Sr 0.18 Ca 0.12 )TiO 3
性能：performance:
d33(pC/N) tg δ(％) ε33/ε0 kp(％) Qm 泊松比d 33 (pC/N) tg δ(%) ε 33 /ε 0 k p (%) Qm Poisson's ratio
147 2.0 729 29.7 153 0.292147 2.0 729 29.7 153 0.292
实施例2：Example 2:
配方：formula:
0.935Bi0.3Na0.7TiO3+0.065(Ba0.62Sr0.23Ca0.15)TiO3 0.935Bi 0.3 Na 0.7 TiO 3 +0.065(Ba 0.62 Sr 0.23 Ca 0.15 )TiO 3
性能：performance:
d33(pC/N) tgδ(％) ε33/ε0 kp(％) Qm 泊松比d 33 (pC/N) tgδ(%) ε 33 /ε 0 k p (%) Qm Poisson's ratio
105 1.2 502 27.0 258 0.292105 1.2 502 27.0 258 0.292
实施例3：Example 3:
配方：formula:
[0.9Bi0.5Na0.5TiO3+0.1(Ba0.6Sr0.3Ca0.1)TiO3](95wt％)+Li2O(5wt％)[0.9Bi 0.5 Na 0.5 TiO 3 +0.1(Ba 0.6 Sr 0.3 Ca 0.1 )TiO 3 ](95wt%)+Li 2 O(5wt%)
性能：performance:
d33(pC/N) tgδ(％) ε33/ε0 kp(％) Qm 泊松比d 33 (pC/N) tgδ(%) ε 33 /ε 0 k p (%) Qm Poisson's ratio
162 2.5 984 25.4 126 0.295162 2.5 984 25.4 126 0.295
实施例4：Example 4:
配方：formula:
0.895Bi0.4Na0.6TiO3+0.105(Ba0.57Sr0.14Ca0.29)TiO3 0.895Bi 0.4 Na 0.6 TiO 3 +0.105(Ba 0.57 Sr 0.14 Ca 0.29 )TiO 3
性能：performance:
d33(pC/N) tgδ(％) ε33/ε0 kp(％) Qm 泊松比d 33 (pC/N) tgδ(%) ε 33 /ε 0 k p (%) Qm Poisson's ratio
132 2.1 681 30.3 186 0.285132 2.1 681 30.3 186 0.285
实施例5：Example 5:
配方：formula:
[0.915Bi0.5Na0.5TiO3+0.085(Ba0.7Sr0.18Ca0.12)TiO3](92wt％)+Nb2O5(6wt％)+Ta2O5(2wt％)[0.915Bi 0.5 Na 0.5 TiO 3 +0.085(Ba 0.7 Sr 0.18 Ca 0.12 )TiO 3 ](92wt%)+Nb 2 O 5 (6wt%)+Ta 2 O 5 (2wt%)
性能：performance:
d33(pC/N) tgδ(％) ε33/ε0 kp(％) Qm 泊松比d 33 (pC/N) tgδ(%) ε 33 /ε 0 k p (%) Qm Poisson's ratio
155 2.9 876 24.2 123 0.295155 2.9 876 24.2 123 0.295
实施例6：Embodiment 6:
配方：formula:
[0.9Bi0.5Na0.5TiO3+0.1(Ba0.6Sr0.3Ca0.1)TiO3](99wt％)+Na2O(1wt％)[0.9Bi 0.5 Na 0.5 TiO 3 +0.1(Ba 0.6 Sr 0.3 Ca 0.1 )TiO 3 ](99wt%)+Na 2 O(1wt%)
性能：performance:
d33(pC/N) tg δ(％) ε33/ε0 kp(％) Qm 泊松比d 33 (pC/N) tg δ(%) ε 33 /ε 0 k p (%) Qm Poisson's ratio
152 3.0 964 22.4 120 0.291152 3.0 964 22.4 120 0.291
实施例7：Embodiment 7:
配方：formula:
[0.9Bi0.5Na0.5TiO3+0.1(Ba0.6Sr0.3Ca0.1)TiO3](92wt％)+CeO2(5wt％)+Nb2O5(3wt％)[0.9Bi 0.5 Na 0.5 TiO 3 +0.1(Ba 0.6 Sr 0.3 Ca 0.1 )TiO 3 ](92wt%)+CeO 2 (5wt%)+Nb 2 O 5 (3wt%)
性能：performance:
d33(pC/N) tgδ(％) ε33/ε0 kp(％) Qm 泊松比d 33 (pC/N) tgδ(%) ε 33 /ε 0 k p (%) Qm Poisson's ratio
158 2.9 979 21.4 127 0.294158 2.9 979 21.4 127 0.294
实施例8：Embodiment 8:
配方：formula:
[0.895Bi0.5Na0.5TiO3+0.105(Ba0.57Sr0.14Ca0.29)TiO3](92wt％)+La2O3(8wt％)[0.895Bi 0.5 Na 0.5 TiO 3 +0.105(Ba 0.57 Sr 0.14 Ca 0.29 )TiO 3 ] (92wt%)+La 2 O 3 (8wt%)
性能：performance:
d33(pC/N) tg δ(％) ε33/ε0 kp(％) Qm 泊松比d 33 (pC/N) tg δ(%) ε 33 /ε 0 k p (%) Qm Poisson's ratio
132 2.1 681 30.3 183 0.285132 2.1 681 30.3 183 0.285
实施例9：Embodiment 9:
配方：formula:
[0.9Bi0.5Na0.5TiO3+0.1(Ba0.60Sr0.30Ca0.10)TiO3](95wt％)+Fe2O3(5wt％)[0.9Bi 0.5 Na 0.5 TiO 3 +0.1(Ba 0.60 Sr 0.30 Ca 0.10 )TiO 3 ](95wt%)+Fe 2 O 3 (5wt%)
性能：performance:
d33(pC/N) tgδ(％) ε33/ε0 kp(％) Qm 泊松比d 33 (pC/N) tgδ(%) ε 33 /ε 0 k p (%) Qm Poisson's ratio
148 3.9 961 20.0 147 0.290148 3.9 961 20.0 147 0.290
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