CN101239824B - Sodium potassium niobate barium zirconate titanate series lead-free piezoelectric ceramic composition - Google Patents

Sodium potassium niobate barium zirconate titanate series lead-free piezoelectric ceramic composition Download PDF

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CN101239824B
CN101239824B CN2007100067872A CN200710006787A CN101239824B CN 101239824 B CN101239824 B CN 101239824B CN 2007100067872 A CN2007100067872 A CN 2007100067872A CN 200710006787 A CN200710006787 A CN 200710006787A CN 101239824 B CN101239824 B CN 101239824B
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CN101239824A (en
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赁敦敏
郭建荣
陈王丽华
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Hong Kong Polytechnic University HKPU
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Abstract

The present invention provides a novel potassium-sodium niobate zirconium barium titanate series leadless piezoelectric ceramic composition which comprises perovskite type piezoelectrics K<1-x>Na<x>NbO3 and strong ferroelectrics Ba(Ti<1-y>Zr<y>)O3, the general formula is represented by (1-z)(K<1-x>Na<x>)NbO3-zBa(Ti<1-y>Zr<y>)O3, in the formula 0<x<1, 0<y<1, 0<z<=0.1. The leadless piezoelectric ceramic composition can also comprises one or a plurality of oxides, the general formula is (1-z)(k<1-x>Na<x>)NbO3-zBa(Ti<1-y> Zr<y>)O3((100-a)mol%+M<alpha>O<beta>(amol%). The optimal value d33 of the system piezoelectric ceramic composition can up to above 230pC/N, kp can up to above 48%, and the kt can up to above 47%, has the advantages of good compactness, high Curie temperature, good thermal stability, being prepared with the conventional piezoelectric ceramic preparing technique and has practicability.

Description

Sodium potassium niobate barium zirconate titanate series lead-free piezoelectric ceramic composition
Technical field
The invention belongs to perovskite structure piezoelectric ceramics field, relate to a kind of novel polynary system columbate leadless piezoelectric ceramic composition, particularly relate to a kind of sodium potassium niobate barium zirconate titanate series lead-free piezoelectric ceramic composition.
Background technology
From the piezoelectricity of middle 1940s discovery barium titanate ceramics, particularly have Pb-based lanthanumdoped zirconate titanates Pb (Ti, Zr) O of excellent piezoelectric property and high-curie temperature 3After pottery was succeeded in developing, constitutional features was ABO 3The research and development of the lead-based perovskite piezoelectric ceramics of type are very active, and piezoelectric ceramics and piezoelectric ceramic devices have been widely used in particularly information industry field of industry.With (Pb (Ti, Zr) O 3) for the lead base two component system of representative with Pb-based lanthanumdoped zirconate titanates (Pb (Ti, Zr) O 3) be base, add the 3rd constituent element [as with lead magnoniobate (Pb (Mg 1/3Nb 2/3) O 3) for representative] and the lead base ternary system piezoelectric ceramic have good piezoelectricity ferro performance, high Curie temperature.The piezoelectric ceramics overwhelming majority who uses in the industrial production is such lead base piezoelectric ceramics.
But, in the lead base piezoceramic material, PbO or Pb 3O 4Content account for 70% of raw material total amount.Lead contamination has become one of human public hazards.The lead base piezoelectric ceramics produce, use and discarded last handling process in cause serious harm for the mankind and ecotope, be unfavorable for the Sustainable development of human society.In recent years, exploitation piezoelectric ceramics system lead-free, superior performance is subjected to the particularly pay attention to day by day of America and Europe, Japan, Korea S and China of countries in the world.
The unleaded base piezoelectric ceramic system of broad research has four classes at present: bismuth laminated leadless piezoelectric ceramic, BaTiO 3Based leadless piezoelectric ceramics, Bi 0.5Na 0.5TiO 3Based leadless piezoelectric ceramics and base metal niobate leadless piezoelectric ceramics.Bismuth laminated leadless piezoelectric ceramic Curie temperature height, anisotropy is big, but piezoelectric activity is low; BaTiO 3The base piezoelectric ceramic Curie temperature is 120 ℃ only, and piezoelectric property is medium; Bi 0.5Na 0.5TiO 3It is strong and be easy to modification and improve piezoelectric property that based leadless piezoelectric ceramics has piezoelectricity, but near second phase transformation 210 ℃ causes the umpolarization temperature to be lower than 210 ℃, often follows the serious reduction of umpolarization temperature when modification improves piezoelectric property; The base metal niobate leadless piezoelectric ceramics is difficult to obtain fine and close pottery by the traditional ceramics technology of preparing, becomes leadless piezoelectric ceramics research focus but it has the Curie temperature up to 420 ℃.
K 1-xNa xNbO 3Be ferroelectrics KNbO 3With antiferroelectric NaNbO 3Solid solution and the ABO that forms 3The perovskite typed ferroelectrics has that ferroelectricity is strong, Curie temperature is high and advantage such as electromechanical coupling factor is big.But as mentioned above, traditional ceramics technology can not make fine and close high performance K 1-xNa xNbO 3Document 1 (J.Am.Ceram.Soc.42 (9), 438 (1959)) has provided the K of traditional ceramics prepared 0.5Na 0.5NbO 3Pottery, d 33=80pC/N, k p=0.36, T c=420 ℃, ρ=4.25g/cm 3Document 2 (J.Am.Ceram.Soc.45 (5), 209 (1962)) has provided hot pressed K 0.5Na 0.5NbO 3Pottery, d 33=160pC/N, k p=0.45, ρ=4.46g/cm 3It is K that document 3 (Appl.Phys.Lett.85,4121 (2004)) has provided composition formula 0.5Na 0.5NbO 3-LiNbO 3The leadless piezoelectric ceramics system, d 33=230pC/N, k p=44%; It is K that document 4 (Mater.Lett.59,241 (2005)) has provided composition formula 0.5Na 0.5NbO 3-LiTaO 3The leadless piezoelectric ceramics system, d 33=200pC/N, k p=0.36%; Document 5 (piezoelectricity and acousto-optic, Vol.28, No.1, p60) having provided composition formula is K 0.5Na 0.5NbO 3-LiTaO 3The leadless piezoelectric ceramics system, d 33=134pC/N, k p=33%.Make fine and close high performance columbate leadless piezoelectric ceramic composition as traditional ceramics manufacturing process how and become the problem that present stage need solve.
Summary of the invention
The object of the present invention is to provide a kind of sodium potassium niobate barium zirconate titanate series lead-free piezoelectric ceramic composition, to solve the problems referred to above that prior art exists.Composition provided by the present invention has overcome the inherent defective of existing lead base piezoelectric ceramics system own, and has improved existing base metal niobate leadless piezoelectric ceramics performance.Such lead-free piezoelectric ceramic composition adopts the traditional ceramics prepared, and it is good to have compactness, and piezoelectric property is good, the Curie temperature height, and Heat stability is good has practicality.
Sodium potassium niobate barium zirconate titanate series lead-free piezoelectric ceramic composition provided by the present invention comprises perovskite typed piezoelectrics K 1-xNa xNbO 3With strong ferroelectrics Ba (Ti 1-yZr y) O 3According to K 1-xNa xNbO 3Inherent characteristics own and the accurate homotype phase boundary theory of lead base pottery, the present invention is to ABO 3The perovskite typed piezoelectrics K of structure 1-xNa xNbO 3The strong ferroelectrics Ba (Ti of middle introducing 1-yZr y) O 3, reduce K 1-xNa xNbO 3Four directions-quadrature transformation temperature near room temperature and form the two-phase coexistent district, formed a kind of novel perovskite structure lead-free piezoceramic material.
Ceramic composition provided by the present invention can be used general formula (1-z) (K 1-xNa x) NbO 3-zBa (Ti 1-yZr y) O 3Represent that x, y, z represent the atomicity that respective element is shared, i.e. atomic percent, 0<x in the formula<1,0<y<1,0<z≤0.1.
In addition, can also further contain one or more oxide compounds in the sodium potassium niobate barium zirconate titanate series lead-free piezoelectric ceramic composition of the present invention, then the general formula of composition is (1-z) (K 1-xNa x) NbO 3-zBa (Ti 1-yZr y) O 3((100-a) mol%)+M αO β(amol%), M in formula αO βExpression oxide compound, α and β are represented the atomicity of corresponding element M and oxygen in the relevant oxide compound respectively, and amol% accounts for the overall mol ratio of composition, wherein 0<a≤3 for this oxide compound.M is that+1 valency is to+6 valencys, oxygen is-divalent, M is the element that can form solid-oxide with oxygen, and it includes but not limited to the element of at least a Na of being selected from, 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 and Ag.Preferred M is one or more elements among Mn, Cu, the Bi.
The piezoceramic material that the present invention proposes can also be added oxide compound (being base-material+hotchpotch) to be made up of the base-material that the front general formula is represented, makes some optimizing performance parameters.Can be expressed as with general formula: (1-z) (K 1-xNa x) NbO 3-zBa (Ti 1-yZr y) O 3+ aM αO β(mol%), M in formula αO βThe expression hotchpotch, the shared proportion of hotchpotch is 0-3mol%.M αO βBe one or more doping oxides, M is for+1-+6 valency and can form the element of solid-oxide with oxygen, as etc., α and β represent the atomicity of corresponding element M and oxygen in the relevant oxide compound respectively.
Sodium potassium niobate barium zirconate titanate series lead-free piezoelectric ceramic composition of the present invention has good piezoelectric property and high Curie temperature, through material properties test, and piezoelectric constant d 33Can reach more than 230 pC/N electromechanical coupling factor k pCan reach more than 0.48 electromechanical coupling factor k tCan reach more than 47% Curie temperature T cBe 233-424 ℃.The advantage of composition provided by the invention is: compactness is good; Piezoelectric property is good; The Curie temperature height; The piezoelectric property Heat stability is good; Stable preparation process adopts the conventional piezoelectric ceramics processing to obtain; Sintering temperature is low, is about 1090-1150 ℃.By further containing oxide compound, some performance perameters of this lead-free piezoelectric ceramic composition are optimized.
Description of drawings
Fig. 1 is the 0.94 (K that the present invention records 0.5Na 0.5) NbO 3-0.06Ba (Ti 0.95Zr 0.05) O 3(99mol%)+MnO 2(1mol%) leadless piezoelectric ceramics is at 1kHz, the specific inductivity of 10kHz and 100kHz (ε)-temperature (T) curve;
Fig. 2 is the 0.94 (K that the present invention records 0.5Na 0.5) NbO 3-0.06Ba (Ti 0.95Zr 0.05) O 3((100-a) mol%)+MnO 2(a mol%) leadless piezoelectric ceramics ferroelectric hysteresis loop (a=0.25,0.5 and 0.75) at room temperature;
Fig. 3 is the 0.94 (K that the present invention records 0.5Na 0.5) NbO 3-0.06Ba (Ti 0.95Zr 0.05) O 3(99mol%)+MnO 2(1mol%) leadless piezoelectric ceramics is at 1 hour piezoelectric constant d of each selected temperature annealing 33Value.
Fig. 4 is the 0.94 (K that the present invention records 0.5Na 0.5) NbO 3-0.06Ba (Ti 0.95Zr 0.05) O 3(100-amol%)+MnO 2(amol%) MnO in the pottery 2Doping to the influence of density (ρ).
Embodiment
Below will describe the present invention by embodiment, these embodiment are property illustrative purposes presented for purpose of illustration just, and is not to be used to limit the present invention.
Preparing general formula of the present invention is (1-z) (K 1-xNa x) NbO 3-zBa (Ti 1-yZr y) O 3Leadless piezoelectric ceramics can adopt technical pure or chemical pure Na 2CO 3, K 2CO 3, Nb 2O 5, BaCO 3, TiO 2, ZrO 2Be raw material, make according to conventional preparation method.For example, a kind of method wherein is the stoichiometric ratio raw materials weighing according to general formula, behind abundant ball milling mixing, pack in the alumina crucible, carry out pre-burning at 800-900 ℃, soaking time is 6 hours, adding additives, moulding, plastic removal again are at last at 1090-1150 ℃ of following sintering 2-6 hour.Ceramic plate behind the sintering is by last silver electrode, and in 150-200 ℃ silicone oil, polarization is 30-40 minute under the voltage of 5-6kV/mm.
Preparing general formula of the present invention is (1-z) (K 1-xNa x) NbO 3-zBa (Ti 1-yZr y) O 3((100-a) mol%)+M αO βA kind of method of leadless piezoelectric ceramics (amol%) is to adopt technical pure or chemical pure Na 2CO 3, K 2CO 3, Nb 2O 5, BaCO 3, TiO 2, ZrO 2Be raw material, by the stoichiometric ratio raw materials weighing of its general formula, behind abundant ball milling mixing, in the alumina crucible of packing into, carry out pre-burning at 800-900 ℃, soaking time is 6 hours.Add the pure or chemical pure M of appropriate amount of industrial in the pre-burning synthetic powder αO βProperty-modifying additive, levigate through ball milling again, thorough mixing, adding additives, moulding, plastic removal are at last at 1090-1150 ℃ of following sintering 2-6 hour.Ceramic plate behind the sintering is by last silver electrode, and in 150-200 ℃ silicone oil, polarization is 30-40 minute under the voltage of 5-6kV/mm.
The prescription of Zhi Bei leadless piezoelectric ceramics and performance index are as follows according to the method described above:
Embodiment 1:
Prescription: 0.94 (K 0.5Na 0.5) NbO 3-0.06Ba (Ti 0.95Zr 0.05) O 3
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) Tc(℃)
109 1094 21.2 25.6 314
Embodiment 2:
Prescription:
0.96(K 0.5Na 0.5)NbO 3-0.04Ba(Ti 0.95Zr 0.05)O 3(99mol%)+MnO 2(1mol%)
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) T c(℃)
120 861 39.5 41.0 352
Embodiment 3:
Prescription:
0.93(K 0.5Na 0.5)NbO 3-0.07Ba(Ti 0.95Zr 0.05)O 3(99mol%)+MnO 2(1mol%)
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) T c(℃)
179 1157 39.5 41.9 291
Embodiment 4:
Prescription:
0.94(K 0.5Na 0.5)NbO 3-0.06Ba(Ti 0.95Zr 0.05)O 3(99mol%)+MnO 2(1mol%)
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) T c(℃)
234 1191 48.3 47.8 318
Embodiment 5:
Prescription:
0.94(K 0.5Na 0.5)NbO 3-0.06Ba(Ti 0.95Zr 0.05)O 3(99.5mol%)+MnO 2(0.5mol%)
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) T c(℃)
225 1358 47.3 45.3 315
Embodiment 6:
Prescription:
0.94(K 0.5Na 0.5)NbO 3-0.06Ba(Ti 0.95Zr 0.05)O 3(99.5mol%)+CuO(0.5mol%)
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) T c(℃)
176 1096 38.7 34.9 313
Embodiment 7:
Prescription:
0.94(K 0.5Na 0.5)NbO 3-0.06Ba(Ti 0.95Zr 0.05)O 3(98.75mol%)+CuO(1.25mol%)
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) T c(℃)
180 890 48.8 49.5 315
Embodiment 8:
Prescription:
0.94(K 0.5Na 0.5)NbO 3-0.06Ba(Ti 0.95Zr 0.05)O 3(98.75mol%)+CuO(0.5mol%)+MnO 2(0.75mol%)
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) T c(℃)
215 1010 44.5 45.6 320
Embodiment 9:
Prescription:
0.94(K 0.5Na 0.5)NbO 3-0.06Ba(Ti 0.90Zr 0.10)O 3(99.25mol%)+MnO 2(0.25mol%)+CuO(0.5mol%)
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) T c(℃)
198 1040 40.6 42.1 308
Embodiment 10:
Prescription:
0.94(K 0.5Na 0.5)NbO 3-0.06Ba(Ti 0.90Zr 0.10)O 3(99.25mol%)+MnO 2(0.25mol%)+Bi 2O 3(0.5mol%)
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) T c(℃)
160 1230 42.3 43.4 316
Embodiment 11:
Prescription:
0.94(K 0.5Na 0.5)NbO 3-0.06Ba(Ti 0.99Zr 0.01)O 3(99mol%)+CuO(1mol%)
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) T c(℃)
187 1145 42.7 47.5 314
Embodiment 12:
Prescription:
0.90(K 0.5Na 0.5)NbO 3-0.10Ba(Ti 0.95Zr 0.05)O 3(99.50mol%)+CuO(0.50mol%)
Performance:
d 33(pC/N) ε 330 k p(%) k t(%) T c(℃)
79 1043 20.3 30.8 186

Claims (3)

1. sodium potassium niobate barium zirconate titanate series lead-free piezoelectric ceramic composition is characterized in that said composition comprises perovskite typed piezoelectrics K 1-xNa xNbO 3With strong ferroelectrics Ba (Ti 1-yZr y) O 3, wherein said composition is by general formula (1-z) (K 1-xNa x) NbO 3-zBa (Ti 1-yZr y) O 3Represent 0<x in the formula<1,0<y<1,0<z≤0.1.
2. lead-free piezoceramic material composition as claimed in claim 1 is characterized in that described composition also contains one or more oxide compounds, and the general formula of composition is (1-z) (K 1-xNa x) NbO 3-zBa (Ti 1-yZr y) O 3((100-a) mol%)+M αO β(amol%), M in formula αO βThe expression oxide compound, α and β represent the atomicity of corresponding element M and oxygen in the relevant oxide compound respectively, amol% accounts for the overall mol ratio of composition for this oxide compound, 0<a≤3 wherein, M for+1 valency to+6 valencys and can form the element of solid-oxide with oxygen, it is selected from least a among 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 and the Ag.
3. lead-free piezoceramic material composition as claimed in claim 2 is characterized in that described M is one or more elements among Mn, Cu and the Bi.
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