CN103482977A - Niobium sodium potassium antimonate-potassium sodium bismuth zirconate leadless piezoelectric ceramic with high piezoelectric constant and preparation method thereof - Google Patents
Niobium sodium potassium antimonate-potassium sodium bismuth zirconate leadless piezoelectric ceramic with high piezoelectric constant and preparation method thereof Download PDFInfo
- Publication number
- CN103482977A CN103482977A CN201310392216.2A CN201310392216A CN103482977A CN 103482977 A CN103482977 A CN 103482977A CN 201310392216 A CN201310392216 A CN 201310392216A CN 103482977 A CN103482977 A CN 103482977A
- Authority
- CN
- China
- Prior art keywords
- sodium
- piezoelectric ceramics
- leadless piezoelectric
- niobium
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to niobium sodium potassium antimonate-potassium sodium bismuth zirconate leadless piezoelectric ceramic with a high piezoelectric constant and a preparation method thereof, which belong to the field of environmental coordinative piezoelectric ceramic of perovskite structures. The leadless piezoelectric ceramic with a general formula of (1-x) (K1-yNay) (Nb1-zSbz) O3 + xBi0.5 (Na1-uKu) 0.5ZrO3 is prepared by a traditional solid state sintering method, wherein in the formula, x is not smaller than 0 while not larger than 0.05, y is not smaller than 0.40 while not larger than 0.68, z is not smaller than 0.02 while not larger than 0.06, and u is not smaller than 0 while not larger than 1; the d33 of the leadless piezoelectric ceramic disclosed by the invention can be as high as 470 pC/N, kp can reach 47%, and Tc is as high as 313 DEG C. Devices prepared by the ceramic can work under high temperatures, so that the ceramic has a practical application value in high-temperature electronic equipment; since the ceramic contains no expensive tantalum element, the price of the used raw materials is low, so that the cost is saved.
Description
Technical field
The present invention relates to a kind of leadless piezoelectric ceramics, particularly a kind of niobium potassium antimonate sodium of high piezoelectric constant-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics and preparation method thereof, belong to perovskite structure environment compatibility piezoelectric ceramics field.
Background technology
The high-performance piezoelectric ceramics is to have hi tech and new material important and widespread use, that international competition is very fierce; This class material and national economy social development, national security, people's quality of life are closely related.The high-performance piezoelectric ceramics has been widely used in the electron devices such as frequency control device, transverter, sensor and stopper.It has very important status and effect in the high and new technology fields relevant to national economy and national security such as photoelectron technology, information technology, accurate control technique, Dynamic Non-Destruction Measurements.Pb-based lanthanumdoped zirconate titanates (the PbZr that grow up the fifties in last century
1-xti
xo
3, PZT) the base pottery is because of its excellent piezoelectric property, as piezoelectric constant d
33up to 450-750pC/N and planar electromechanical coupling factor k
pup to 50-70%, all respects of national economy, defence and national security have been widely used in.The PZT pottery occupies most shares in ferroelectric piezoelectric market, the whole world, yet in this class piezoelectric ceramics, the content of plumbous oxide accounts for 70% of raw material total amount, in the treating processes after it is produced, uses and be discarded, all can cause serious harm to the mankind and ecotope.Along with the raising of people to Natural Survival environmental concern degree, in order to realize the coordinated development of economy, society, environment and resource, nearly ten years, also pay much attention to the research of leadless piezoelectric material material countries in the world, and a series of laws and regulations are put into effect in succession.For example, " electronics and IT products production prevention and cure of pollution management method " that " domestic electronic appliances recovery bill ", China put into effect in 2006 etc. crossed by the European Union of 2003 by RoHS decree, expert on Japan.Just under such international situation, a unleaded research and development tide of the piezoelectric ceramics piezoelectricity field of just have swepting the globe.The research-and-development relationship of high-performance Pb-free piezoelectric ceramics is to a major issue of national destiny and social sustainable development strategy.
In recent years, a large amount of human and material resources have been dropped into and financial resources are studied the high-performance Pb-free piezoelectric in countries in the world.From structure, leadless piezoelectric ceramics mainly is divided into following three classes: tungsten bronze structure, bismuth laminated and perovskite structure.All there are relative merits separately in the leadless piezoelectric system of this three class formation, although as tungsten bronze structure with bismuth laminatedly have a high Curie temperature, its piezoelectric constant is low; Though the leadless piezoelectric ceramics of perovskite structure has higher piezoelectric property and high Curie temperature, up to the present its piezoelectric constant also is difficult to surmount PZT.The piezoelectric property that base metal niobate based leadless piezoelectric ceramic is relatively superior with it and higher Curie temperature and receive much attention, be considered to be expected to most one of leadless piezoelectric ceramics system replaced the lead base piezoelectric ceramics.At present, by room temperature, building quadrature-Tetragonal boundary region, the piezoelectric constant of base metal niobate based leadless piezoelectric ceramic can be promoted to 200～350pC/N.Therefore, the research of the piezoelectric property of lifting base metal niobate based leadless piezoelectric ceramic becomes the theme of current leadless piezoelectric ceramics research.
Summary of the invention
Purpose of the present invention is to strengthen the piezoelectric property of potassium-sodium niobate (KNN) based leadless piezoelectric ceramics just, and a kind of niobium potassium antimonate sodium of high piezoelectric constant-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics is provided, and the preparation method that this leadless piezoelectric ceramics is provided.The niobium potassium antimonate sodium that the method adopts traditional solid sintering technology to prepare-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics, its piezoelectric constant d
33can be up to 470pC/N, planar electromechanical coupling factor k
pcan reach 47%, Curie temperature T
cup to 313 ℃.
For realizing the object of the invention, the technical scheme that the present invention adopts following technical measures to form realizes.
Basic ideas of the present invention are: realize the purpose of niobium potassium antimonate sodium-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics high tension performance by the design and optimization of phase structure, its concrete practice is: add Bi
0.5(Na
1-uk
u)
0.5(0≤u≤1) reduces the high-T_c superconductors temperature of niobium potassium antimonate sodium near room temperature, is reduced in 20～40 ℃ of left and right; Add Zr
4+the tripartite of niobium potassium antimonate sodium-quadrature transformation temperature is promoted to near room temperature, is promoted to 20～40 ℃ of left and right; Simultaneously close to room temperature for the high-T_c superconductors temperature and the tripartite-quadrature transformation temperature that make niobium potassium antimonate sodium-zirconic acid potassium sodium bismuth pottery, therefore introduce Sb; And then prepare and there is the tripartite-the niobium potassium antimonate sodium of cubic novel interphase structure-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics, its general formula is (1-x) (K
1-yna
y) (Nb
1-zsb
z) O
x+ xBi
0.5(Na
1-uk
u)
0.5zrO
3.
The niobium potassium antimonate sodium of a kind of high piezoelectric constant of the present invention-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics, by general formula (1-x) (K
1-yna
y) (Nb
1-zsb
z) O
3+ xBi
0.5(Na
1-uk
u)
0.5zrO
3mean, the x, y, z in formula, u mean the shared atomicity in each constituent element of respective element material in compound ion, i.e. atomic percent; The atomicity summation of all elements should be 1,0≤x in formula≤0.05,0.40≤y≤0.68,0.02≤z≤0.06,0≤u≤1.
The niobium potassium antimonate sodium of high piezoelectric constant of the present invention-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics, its crystal configuration is perovskite structure.
The niobium potassium antimonate sodium of high piezoelectric constant of the present invention-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics, its piezoelectric constant d
33can be up to 470pC/N; Planar electromechanical coupling factor k
pcan be up to 47%; Curie temperature T
ccan be up to 313 ℃.
The preparation method of the above-mentioned arbitrary described niobium potassium antimonate sodium of the present invention-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics comprises following processing step:
(1) adopt traditional solid sintering technology preparation technology, with analytically pure sodium carbonate (Na
2cO
3), or salt of wormwood (K
2cO
3), or Niobium Pentxoxide (Nb
2o
5), or antimonous oxide (Sb
2o
3), or bismuth oxide (Bi
2o
3), or zirconium white (ZrO
2) be raw material, according to (1-x) (K of corresponding system
1-yna
y) (Nb
1-zsb
z) O
3+ xBi
0.5(Na
1-uk
u)
0.5zrO
3prepared burden, 0≤x in formula≤0.05,0.40≤y≤0.68,0.02≤z≤0.06,0≤u≤1;
(2) raw material step (1) prepared is usingd dehydrated alcohol as ball-milling medium, by a rolling ball milling 20-24 hour post-drying, obtains mixed powder;
(3) step (2) gained mixed powder is incubated to pre-burning in 3-6 hour at 800-950 ℃; The polyvinyl alcohol water solution granulation that adds 10wt% in pre-burned powder;
(4) by the powder after step (3) granulation, utilize grinding tool that it is pressed into to sequin binder removal, the sequin after binder removal, at 1-5 hour sintering of 1065～1135 ℃ of insulations, is obtained to ceramic plate;
(5) by the ceramic plate after step (4) heat preservation sintering by upper silver electrode; By the ceramic plate of upper silver, in the silicone oil of 30～150 ℃, using electric field is polarization 10-30 minute under 3-4kV/mm voltage;
(6) after having polarized, described ceramic plate is taken out from silicone oil, obtain the niobium potassium antimonate sodium of high piezoelectric constant-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics sample, in air, after standing 24 hours, then adopt ieee standard to measure the electric property of this leadless piezoelectric ceramics of gained it.
The present invention has the following advantages and useful technique effect:
1, leadless piezoelectric ceramics provided by the invention has the highest up to now piezoelectric property, its piezoelectric constant d
33reach as high as 470pC/N; Planar electromechanical coupling factor k
pcan reach 47%; Curie temperature T
cup to 313 ℃; Piezoelectric constant 200～350pC/N that its piezoelectric constant is compared the current base metal niobate based leadless piezoelectric ceramic in room temperature structure quadrature-Tetragonal boundary region is also high.
2, leadless piezoelectric ceramics provided by the invention is owing to having higher Curie temperature, thereby the device prepared by this pottery can work at higher temperature, thereby has actual using value in high-temperature electronic equipment.
3, leadless piezoelectric ceramics provided by the invention is owing to not containing expensive tantalum element, the [(K suitable with performance
cna
d)
1-eli
e] [Nb
αsb
βta
γ] O
3compare, raw materials used cheap, thereby cost-saving, be conducive to promote practicalization, in industrial production, apply.
4, leadless piezoelectric ceramics provided by the invention can adopt industrial raw material to obtain through the traditional ceramics technology of preparing, its technique simple and stable, easy handling.
The accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 preparation when x=0,0.03,0.04,0.05 changes value, at y=0.52, z=0.05, u=0.18 is (1-x) K during value fixedly
0.48na
0.52(Nb
0.95sb
0.05) O
3-xBi
0.5(Na
0.82k
0.18)
0.5zrO
3the relative permittivity ε of leadless piezoelectric ceramics under 100kHz
rthe variation with temperature curve;
Fig. 2 be the embodiment of the present invention 2 preparation at y=0.40,0.44,0.48,0.52,0.56,0.60,0.64, during 0.68 changing value, at x=0.04, z=0.05, u=0.18 is 0.96 (K during value fixedly
1-yna
y) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3the x ray diffraction collection of illustrative plates of leadless piezoelectric ceramics;
Fig. 3 be the embodiment of the present invention 2 preparation at y=0.40,0.48,0.56,0.64,0.68 while changing value, at x=0.04, z=0.05, u=0.18 is 0.96 (K during value fixedly
1-yna
y) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3the relative permittivity ε of leadless piezoelectric ceramics under 100kHz
rthe variation with temperature curve;
Fig. 4 be the embodiment of the present invention 3 preparation at z=0.02,0.04,0.05,0.06 while changing value, at x=0.04, y=0.52, u=0.18 is 0.96 (K during value fixedly
0.48na
0.52) (Nb
1-zsb
z) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3the relative permittivity ε of leadless piezoelectric ceramics under 100kHz
rthe variation with temperature curve;
Fig. 5 be the embodiment of the present invention 4 preparation at u=0,0.18,0.40,0.60,0.80,1.00 while changing value, at x=0.04, y=0.52, z=0.05 is 0.96 (K during value fixedly
0.48na
0.52) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
1-uk
u)
0.5zrO
3the relative permittivity ε of leadless piezoelectric ceramics under 100kHz
rthe variation with temperature curve.
Embodiment
Below by specific embodiment, niobium potassium antimonate sodium of the present invention-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics is further described; be necessary to be pointed out that at this described embodiment is just for further illustrating of the present invention; but should not be understood as any restriction to protection domain of the present invention, the those of skill in the art in this field can make according to the content of the invention described above improvement and the adjustment of some non-intrinsically safes.
In following examples, provided the niobium potassium antimonate sodium of different components-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics resulting d under concrete preparation process condition
33, k
p, tan δ, ε
rand T
cetc. performance perameter:
Embodiment 1
According to general formula (1-x) (K
1-yna
y) (Nb
1-zsb
z) O
3+ xBi
0.5(Na
1-uk
u)
0.5zrO
3the niobium potassium antimonate sodium meaned-zirconic acid potassium sodium bismuth two component system perovskite typed leadless piezoelectric ceramics content is prepared burden;
Work as x=0, y=0.52, z=0.05, during u=0.18,
Its formula one is: (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3;
Work as x=0.03, y=0.52, z=0.05, during u=0.18,
Its formula two is: 0.97 (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3-0.03Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.52, z=0.05, during u=0.18,
Its formula three is: 0.96 (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3-0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.05, y=0.52, z=0.05, during u=0.18,
Its formula four is: 0.95 (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3-0.05Bi
0.5(Na
0.82k
0.18)
0.5zrO
3.
The preparation of formula one: with analytically pure Na
2cO
3, K
2cO
3, Nb
2o
5and Sb
2o
3for raw material, by the accurate weighing of each raw materials by weight; Load weighted raw material is usingd to dehydrated alcohol as ball-milling medium, by 24 hours post-dryings of rolling ball milling, obtain mixed powder; Gained dry powder, in 850 ℃ of insulations pre-burning in 6 hours, is then added to the polyvinyl alcohol water solution granulation that concentration is 10wt% in pre-burned powder; The grinding tool that is 10mm with diameter after granulation is pressed into sequin under the pressure of 10MPa, and its diameter is 10mm, and thickness is 1mm, and binder removal, by the sequin after binder removal under differing temps, different soaking time sintering, obtain ceramic plate; By the ceramic plate after sintering, by upper silver electrode, and in the silicone oil of differing temps, under 4kV/mm voltage, polarization is 30 minutes.In air, after standing 24 hours, adopt ieee standard to carry out the test of electric property the ceramic plate after polarization.
The preparation of formula two-tetra-: with analytically pure Na
2cO
3, K
2cO
3, Nb
2o
5, Sb
2o
3, Bi
2o
3and ZrO
2for raw material, according to the chemical formula of formula two-tetra-, prepared burden respectively; By the accurate weighing of each raw materials by weight; Other preparation conditions and parameter used are identical with formula one.
Prepared by the present embodiment works as x=0, and 0.03,0.04,0.05 when changing value, y=0.52, z=0.05, u=0.18 (1-x) (K during for fixing value
0.48na
0.52) (Nb
0.95sb
0.05) O
3-xBi
0.5(Na
0.82k
0.18)
0.5zrO
3the relative permittivity ε of leadless piezoelectric ceramics under 100kHz
rthe variation with temperature curve as shown in Figure 1.
In the silicone oil of the present embodiment formula one-tetra-sintering, different soaking time and differing temps under differing temps, polarize, and with the electric property of ieee standard test gained leadless piezoelectric ceramics etc., be shown in Table 1.
Table 1 at ambient temperature, preparation parameter and the electric property of one-tetra-the leadless piezoelectric ceramics of filling a prescription
Embodiment 2
According to general formula (1-x) (K
1-yna
y) (Nb
1-zsb
z) O
3+ xBi
0.5(Na
1-uk
u)
0.5zrO
3the niobium potassium antimonate sodium meaned-zirconic acid potassium sodium bismuth two component system perovskite typed leadless piezoelectric ceramics content is prepared burden;
Work as x=0.04, y=0.40, z=0.05, during u=0.18,
Its formula one is: 0.96 (K
0.60na
0.40) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.44, z=0.05, during u=0.18,
Its formula two is: 0.96 (K
0.56na
0.44) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.48, z=0.05, during u=0.18,
Its formula three is: 0.96 (K
0.52na
0.48) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.52, z=0.05, during u=0.18,
Its formula four is: 0.96 (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.56, z=0.05, during u=0.18,
Its formula five is: 0.96 (K
0.44na
0.56) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.60, z=0.05, during u=0.18,
Its formula six is: 0.96 (K
0.40na
0.60) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.64, z=0.05, during u=0.18,
Its formula seven is: 0.96 (K
0.36na
0.64) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.68, z=0.05, during u=0.18,
Its formula eight is: 0.96 (K
0.32na
0.68) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3.
With analytically pure Na
2cO
3, K
2cO
3, Nb
2o
5, Sb
2o
3, Bi
2o
3and ZrO
2for raw material, according to the chemical formula of corresponding formula one-eight, prepared burden respectively, by the accurate weighing of each raw materials by weight; Load weighted raw material is usingd to dehydrated alcohol as ball-milling medium, obtain dry powder by rolling ball milling 24h post-drying, gained dry powder is incubated to pre-burning in 6 hours at 850 ℃, then add the polyvinyl alcohol water solution granulation that concentration is 10wt% in pre-burned powder, the grinding tool that is 10mm with diameter after granulation is pressed into sequin under the pressure of 10MPa, and binder removal; Sequin after binder removal is obtained to ceramic plate in 3 hours at 1105 ℃ of heat preservation sinterings, ceramic plate after sintering is by upper silver electrode, and put into the silicone oil of 30 ℃, under 4kV/mm voltage, polarization is 30 minutes, after having polarized, described ceramic plate is taken out from silicone oil, in air after standing 24 hours, adopt ieee standard to carry out the test of electric property, its result is as shown in table 2.
Prepared by the present embodiment works as y=0.40, and 0.44,0.48,0.52,0.56,0.60,0.64,0.68 when changing value, x=0.04, z=0.05, the 0.96 (K of u=0.18 during for fixing value
1-yna
y) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3the x ray diffraction collection of illustrative plates of leadless piezoelectric ceramics as shown in Figure 2; 0.96 (K prepared by the present embodiment
1-yna
y) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3the relative permittivity ε of leadless piezoelectric ceramics under 100kHz
rthe variation with temperature curve as shown in Figure 3.
Table 2 at ambient temperature, the electric property of one-eight the leadless piezoelectric ceramics of filling a prescription
| y | d 33(pC/N) | k p | tanδ(10kHz) | ε r(10kHz) | T C(℃) |
| 0.40 | 174 | 0.26 | 0.053 | 2854 | 217 |
| 0.44 | 210 | 0.30 | 0.063 | 2802 | 217 |
| 0.48 | 320 | 0.41 | 0.046 | 3143 | 226 |
| 0.52 | 470 | 0.47 | 0.038 | 2756 | 227 |
| 0.56 | 467 | 0.46 | 0.036 | 3091 | 217 |
| 0.60 | 456 | 0.45 | 0.039 | 3131 | 222 |
| 0.64 | 408 | 0.42 | 0.046 | 2686 | 227 |
[0067]?
| 0.68 | 90 | 0.19 | 0.126 | 1968 | 230 |
Embodiment 3
According to general formula (1-x) (K
1-yna
y) (Nb
1-zsb
z) O
3+ xBi
0.5(Na
1-uk
u)
0.5zrO
3the niobium potassium antimonate sodium meaned-zirconic acid potassium sodium bismuth two component system perovskite typed leadless piezoelectric ceramics content is prepared burden;
Work as x=0.04, y=0.52, z=0.02, during u=0.18,
Its formula one is: 0.96 (K
0.48na
0.52) (Nb
0.98sb
0.02) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.52, z=0.03, during u=0.18,
Its formula two is: 0.96 (K
0.48na
0.52) (Nb
0.97sb
0.03) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.52, z=0.04, during u=0.18,
Its formula three is: 0.96 (K
0.48na
0.52) (Nb
0.96sb
0.04) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.52, z=0.05, during u=0.18,
Its formula four is: 0.96 (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.52, z=0.06, during u=0.18,
Its formula five is: 0.96 (K
0.48na
0.52) (Nb
0.94sb
0.06) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3.
With analytically pure Na
2cO
3, K
2cO
3, Nb
2o
5, Sb
2o
3, Bi
2o
3and ZrO
2for raw material, according to the chemical formula of corresponding formula one-five, prepared burden respectively, by the accurate weighing of each raw materials by weight; Load weighted raw material is usingd to dehydrated alcohol as ball-milling medium, with different Ball-milling Time rolling ball millings, the ball milling post-drying obtains dry powder, gained dry powder is incubated to pre-burning in 3-6 hour in differing temps, then add the polyvinyl alcohol water solution granulation that concentration is 10wt% in pre-burned powder, the grinding tool that is 10mm with diameter after granulation is pressed into sequin under the pressure of 10MPa, and binder removal; Finally the sequin of binder removal heat preservation sintering under differing temps is obtained to ceramic plate in 3 hours, by the ceramic plate after sintering by upper silver electrode, and put into the silicone oil of 30 ℃, under 4kV/mm voltage, polarization is 30 minutes, after having polarized, described ceramic plate is taken out from silicone oil, in air after standing 24 hours, adopt ieee standard to carry out the test of electric property, measuring result is as shown in table 3.
The present embodiment prepare at z=0.02,0.03,0.04,0.05,0.06 while getting changing value, x=0.04, y=0.52, the relative permittivity ε of leadless piezoelectric ceramics when u=0.18 gets fixed value under 100kHz
rthe variation with temperature curve as shown in Figure 4.
Electric property of the described different Ball-milling Times of the present embodiment, differing temps and different soaking time pre-burning and one-five the leadless piezoelectric ceramics of filling a prescription etc., be shown in Table 3.
Table 3 at ambient temperature, preparation parameter and the electric property of one-five the leadless piezoelectric ceramics of filling a prescription
Embodiment 4
According to general formula (1-x) (K
1-yna
y) (Nb
1-zsb
z) O
3+ xBi
0.5(Na
1-uk
u)
0.5zrO
3the niobium potassium antimonate sodium meaned-zirconic acid potassium sodium bismuth two component system perovskite typed leadless piezoelectric ceramics content is prepared burden;
Work as x=0.04, y=0.52, z=0.05, during u=0,
Its formula one is: 0.96 (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5na
0.5zrO
3;
Work as x=0.04, y=0.52, z=0.05, during u=0.18,
Its formula two is: 0.96 (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.82k
0.18)
0.5zrO
3;
Work as x=0.04, y=0.52, z=0.05, during u=0.40,
Its formula three is: 0.96 (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.60k
0.40)
0.5zrO
3;
Work as x=0.04, y=0.52, z=0.05, during u=0.60,
Its formula four is: 0.96 (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.40k
0.60)
0.5zrO
3;
Work as x=0.04, y=0.52, z=0.05, during u=0.80,
Its formula five is: 0.96 (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
0.20k
0.80)
0.5zrO
3;
Work as x=0.04, y=0.52, z=0.05, during u=1.00,
Its formula six is: 0.96 (K
0.48na
0.52) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5k
0.5zrO
3.
With analytically pure Na
2cO
3, K
2cO
3, Nb
2o
5, Sb
2o
3, Bi
2o
3and ZrO
2for raw material, according to the chemical formula of corresponding formula one-six, prepared burden respectively, by the accurate weighing of each raw materials by weight; Load weighted raw material is usingd to dehydrated alcohol as ball-milling medium, obtain dry powder by rolling ball milling 20h post-drying, gained dry powder is incubated to pre-burning in 6 hours at 850 ℃, then add the polyvinyl alcohol water solution granulation that concentration is 10wt% in pre-burned powder, the grinding tool that is 10mm with diameter after granulation is pressed into sequin under the pressure of 10 MPa, and binder removal; Finally the sequin after binder removal is obtained to ceramic plate in 3 hours at 1105 ℃ of heat preservation sinterings, by the ceramic plate after sintering by upper silver electrode, and put into the silicone oil of 30 ℃, at different polarized electric fields and dwell time, polarized, after having polarized, described ceramic plate is taken out from silicone oil, in air after standing 24 hours, adopt ieee standard to carry out the test of electric property, its result is as shown in table 4.
The present embodiment prepare at u=0,0.18,0.40,0.60,0.80,1.00 while changing value, at x=0.04, y=0.52, z=0.05 is 0.96 (K during value fixedly
0.48na
0.52) (Nb
0.95sb
0.05) O
3+ 0.04Bi
0.5(Na
1-uk
u)
0.5zrO
3the relative permittivity ε of leadless piezoelectric ceramics under 100kHz
rthe variation with temperature curve as shown in Figure 5.
The present embodiment is in different polarized electric fields, different polarization time, and the electric property of the leadless piezoelectric ceramics of formula one-six etc., be shown in Table 4.
Table 4 at ambient temperature, different polarization parameters and the electric property of one-six the leadless piezoelectric ceramics of filling a prescription
The niobium potassium antimonate sodium prepared through the above embodiment of the present invention-zirconic acid potassium sodium bismuth two component system perovskite typed leadless piezoelectric ceramics, its piezoelectric property listed result from table can see, its piezoelectric constant is the potassium niobate sodium base leadless piezoelectricity pottery that has up to now the highest piezoelectric constant.The chemical constitution formula of this material (1-x) (K
1-yna
y) (Nb
1-zsb
z) O
3+ xBi
0.5(Na
1-uk
u)
0.5zrO
3, work as x=0.04, y=0.52, z=0.05, during u=0.18, the piezoelectric constant d of described potassium niobate sodium-based leadless piezoelectric ceramic
33can be up to～470pC/N, planar electromechanical coupling factor k
pcan reach 47%, Curie temperature T
ccan reach 227 ℃.Thereby the device prepared by this leadless piezoelectric ceramics can work under higher working temperature, there is actual using value in high-temperature electronic equipment.
Claims (4)
1. the niobium potassium antimonate sodium of a high piezoelectric constant-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics, is characterized in that it is by general formula (1-x) (K
1-yna
y) (Nb
1-zsb
z) O
3+ xBi
0.5(Na
1-uk
u)
0.5zrO
3mean, the x, y, z in formula, u mean the shared atomicity in each constituent element of respective element material in compound ion, i.e. atomic percent; The atomicity summation of all elements should be 1,0≤x in formula≤0.05,0.40≤y≤0.68,0.02≤z≤0.06,0≤u≤1.
2. the niobium potassium antimonate sodium of high piezoelectric constant-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics according to claim 1, is characterized in that its crystal configuration is perovskite structure.
3. according to the niobium potassium antimonate sodium of claim 1 or 2 described high piezoelectric constant-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics, it is characterized in that the piezoelectric constant d of this two component system leadless piezoelectric ceramics
33up to 470pC/N; Planar electromechanical coupling factor k
pup to 47%; Curie temperature T
cup to 313 ℃.
4. the preparation method of the niobium potassium antimonate sodium of the described high piezoelectric constant of claim 1-3 any one-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics is characterized in that comprising following processing step:
(1) adopt traditional solid sintering technology preparation technology, with analytically pure sodium carbonate, or salt of wormwood, or Niobium Pentxoxide, or antimonous oxide, or bismuth oxide, or zirconium white is raw material, according to (1-x) (K of corresponding system
1-yna
y) (Nb
1-zsb
z) O
3+ xBi
0.5(Na
1-uk
u)
0.5zrO
3prepared burden;
(2) raw material step (1) prepared is usingd dehydrated alcohol as ball-milling medium, by a rolling ball milling 20-24 hour post-drying, obtains mixed powder;
(3) step (2) gained mixed powder is incubated to pre-burning in 3-6 hour at 800-950 ℃; The polyvinyl alcohol water solution granulation that adds 10wt% in pre-burned powder;
(4) by the powder after step (3) granulation, utilize grinding tool that it is pressed into to sequin binder removal; Sequin after binder removal, at 1-5 hour sintering of 1065～1135 ℃ of insulations, is obtained to ceramic plate;
(5) by the ceramic plate after step (4) sintering by upper silver electrode; By the ceramic plate of upper silver, in the silicone oil of 30～150 ℃, using electric field is polarization 10-30 minute under 3-4kV/mm voltage;
(6) after having polarized, described ceramic plate is taken out from silicone oil, obtain the niobium potassium antimonate sodium of high piezoelectric constant-zirconic acid potassium sodium bismuth two component system leadless piezoelectric ceramics, by its in air standing 24 hours, then adopt ieee standard to measure the electric property of this leadless piezoelectric ceramics of gained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310392216.2A CN103482977A (en) | 2013-09-02 | 2013-09-02 | Niobium sodium potassium antimonate-potassium sodium bismuth zirconate leadless piezoelectric ceramic with high piezoelectric constant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310392216.2A CN103482977A (en) | 2013-09-02 | 2013-09-02 | Niobium sodium potassium antimonate-potassium sodium bismuth zirconate leadless piezoelectric ceramic with high piezoelectric constant and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103482977A true CN103482977A (en) | 2014-01-01 |
Family
ID=49823640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310392216.2A Pending CN103482977A (en) | 2013-09-02 | 2013-09-02 | Niobium sodium potassium antimonate-potassium sodium bismuth zirconate leadless piezoelectric ceramic with high piezoelectric constant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103482977A (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198417A (en) * | 2015-09-08 | 2015-12-30 | 四川大学 | Preparation method of zirconic acid sodium bismuthide lithium cerium doped potassium-sodium niobate based ceramic material |
| CN105837210A (en) * | 2016-03-23 | 2016-08-10 | 四川大学 | Antimony potassium-sodium niobate leadless piezoelectric ceramics and preparation method thereof |
| CN106116576A (en) * | 2016-07-25 | 2016-11-16 | 北京中科奥倍超声波技术研究院 | A kind of KNNS BNZSx leadless piezoelectric material material |
| CN107098701A (en) * | 2017-04-27 | 2017-08-29 | 成都信息工程大学 | Potassium-sodium niobate lithium zirconic acid potassium sodium bismuth scandium acid bismuth ternary series lead-free piezoelectric ceramic |
| CN107268084A (en) * | 2016-04-08 | 2017-10-20 | 中国科学院上海硅酸盐研究所 | Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method |
| CN109608195A (en) * | 2018-12-26 | 2019-04-12 | 同济大学 | The lead-free piezoceramic material and preparation method thereof of electrical, the high electric field induced strain of high pressure |
| CN109626988A (en) * | 2019-01-29 | 2019-04-16 | 同济大学 | High pressure electroresponse and the piezoceramic material of high-curie temperature and preparation method thereof |
| CN110372372A (en) * | 2019-07-31 | 2019-10-25 | 贵州大学 | The preparation method of the bismuth-sodium titanate base lead-free piezoelectric ceramic of low-dielectric loss under high temperature |
| CN110713383A (en) * | 2019-10-25 | 2020-01-21 | 四川大学 | Piezoelectric ceramic material and preparation method thereof |
| CN111302797A (en) * | 2020-02-17 | 2020-06-19 | 四川大学 | Potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method thereof |
| CN111548155A (en) * | 2020-03-31 | 2020-08-18 | 成都迪迈斯科技有限公司 | High-voltage high-Curie-point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic and preparation method thereof |
| CN111908917A (en) * | 2019-05-07 | 2020-11-10 | 四川大学 | Sodium bismuth zirconate strontium doped potassium sodium niobate based piezoelectric ceramic material and preparation method thereof |
| CN111925209A (en) * | 2020-08-10 | 2020-11-13 | 国网河南省电力公司电力科学研究院 | Lead-free sound vibration piezoelectric transduction material and preparation method thereof |
| CN112469682A (en) * | 2018-04-21 | 2021-03-09 | 西安交通大学 | Method for obtaining lead-free piezoelectric material and corresponding lead-free piezoelectric material |
| CN113461422A (en) * | 2021-08-03 | 2021-10-01 | 四川大学 | High-voltage anti-fatigue potassium-sodium niobate-based lead-free piezoelectric ceramic and preparation method thereof |
| CN113666744A (en) * | 2021-09-17 | 2021-11-19 | 四川大学 | Component gradient potassium sodium niobate based leadless piezoelectric ceramic and preparation method thereof |
| CN114262228A (en) * | 2021-11-26 | 2022-04-01 | 广东奥迪威传感科技股份有限公司 | Potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method and application thereof |
| CN114478006A (en) * | 2021-12-31 | 2022-05-13 | 中南大学 | KNNS-BNZ + CuO piezoceramic material and preparation method and application thereof |
| CN114621009A (en) * | 2022-03-16 | 2022-06-14 | 南京理工大学 | Lead magnesium niobate-lead titanate-based piezoelectric ceramic material and preparation method thereof |
| CN115093221A (en) * | 2022-07-11 | 2022-09-23 | 广州凯立达电子股份有限公司 | Potassium-sodium niobate-based leadless piezoelectric ceramic sheet, preparation method and application |
| CN115572165A (en) * | 2021-06-21 | 2023-01-06 | 四川大学 | Niobium zirconium acid bismuth potassium sodium copper iron leadless piezoelectric ceramic with high mechanical quality factor |
| CN116606139A (en) * | 2022-02-08 | 2023-08-18 | 成都理想境界科技有限公司 | Piezoelectric ceramic and preparation method and application thereof |
-
2013
- 2013-09-02 CN CN201310392216.2A patent/CN103482977A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| XIAOJING CHEN ET AL.: "Giant d33 in (K,Na)(Nb,Sb)O3-(Bi,Na,K,Li)ZrO3 based lead–free piezoelectrics with high Tc", 《APPLIED PHYSICS LETTERS》 * |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198417A (en) * | 2015-09-08 | 2015-12-30 | 四川大学 | Preparation method of zirconic acid sodium bismuthide lithium cerium doped potassium-sodium niobate based ceramic material |
| CN105837210A (en) * | 2016-03-23 | 2016-08-10 | 四川大学 | Antimony potassium-sodium niobate leadless piezoelectric ceramics and preparation method thereof |
| CN105837210B (en) * | 2016-03-23 | 2019-03-19 | 四川大学 | Niobium potassium antimonate sodium system leadless piezo-electric ceramic and preparation method thereof |
| CN107268084A (en) * | 2016-04-08 | 2017-10-20 | 中国科学院上海硅酸盐研究所 | Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method |
| CN107268084B (en) * | 2016-04-08 | 2019-10-15 | 中国科学院上海硅酸盐研究所 | Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method |
| CN106116576A (en) * | 2016-07-25 | 2016-11-16 | 北京中科奥倍超声波技术研究院 | A kind of KNNS BNZSx leadless piezoelectric material material |
| CN107098701A (en) * | 2017-04-27 | 2017-08-29 | 成都信息工程大学 | Potassium-sodium niobate lithium zirconic acid potassium sodium bismuth scandium acid bismuth ternary series lead-free piezoelectric ceramic |
| CN107098701B (en) * | 2017-04-27 | 2020-09-08 | 成都信息工程大学 | Potassium sodium lithium niobate-potassium sodium bismuth zirconate-bismuth acid bismuth ternary system lead-free piezoelectric ceramic |
| CN112469682A (en) * | 2018-04-21 | 2021-03-09 | 西安交通大学 | Method for obtaining lead-free piezoelectric material and corresponding lead-free piezoelectric material |
| CN109608195A (en) * | 2018-12-26 | 2019-04-12 | 同济大学 | The lead-free piezoceramic material and preparation method thereof of electrical, the high electric field induced strain of high pressure |
| CN109608195B (en) * | 2018-12-26 | 2021-12-31 | 同济大学 | High-piezoelectricity and high-electrostriction leadless piezoelectric ceramic material and preparation method thereof |
| CN109626988B (en) * | 2019-01-29 | 2021-10-08 | 同济大学 | Piezoelectric ceramic material with high piezoelectric response and high Curie temperature and preparation method thereof |
| CN109626988A (en) * | 2019-01-29 | 2019-04-16 | 同济大学 | High pressure electroresponse and the piezoceramic material of high-curie temperature and preparation method thereof |
| CN111908917A (en) * | 2019-05-07 | 2020-11-10 | 四川大学 | Sodium bismuth zirconate strontium doped potassium sodium niobate based piezoelectric ceramic material and preparation method thereof |
| CN110372372B (en) * | 2019-07-31 | 2021-12-17 | 贵州大学 | Preparation method of sodium bismuth titanate-based lead-free piezoelectric ceramic with low dielectric loss at high temperature |
| CN110372372A (en) * | 2019-07-31 | 2019-10-25 | 贵州大学 | The preparation method of the bismuth-sodium titanate base lead-free piezoelectric ceramic of low-dielectric loss under high temperature |
| CN110713383B (en) * | 2019-10-25 | 2020-07-31 | 四川大学 | Piezoelectric ceramic material and preparation method thereof |
| CN110713383A (en) * | 2019-10-25 | 2020-01-21 | 四川大学 | Piezoelectric ceramic material and preparation method thereof |
| CN111302797A (en) * | 2020-02-17 | 2020-06-19 | 四川大学 | Potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method thereof |
| CN111548155A (en) * | 2020-03-31 | 2020-08-18 | 成都迪迈斯科技有限公司 | High-voltage high-Curie-point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic and preparation method thereof |
| CN111548155B (en) * | 2020-03-31 | 2022-06-24 | 成都迪迈斯科技有限公司 | High-voltage high-Curie-point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic and preparation method thereof |
| CN111925209A (en) * | 2020-08-10 | 2020-11-13 | 国网河南省电力公司电力科学研究院 | Lead-free sound vibration piezoelectric transduction material and preparation method thereof |
| CN115572165A (en) * | 2021-06-21 | 2023-01-06 | 四川大学 | Niobium zirconium acid bismuth potassium sodium copper iron leadless piezoelectric ceramic with high mechanical quality factor |
| CN115572165B (en) * | 2021-06-21 | 2023-08-29 | 四川大学 | Bismuth potassium sodium copper iron niobate leadless piezoelectric ceramic with high mechanical quality factor |
| CN113461422A (en) * | 2021-08-03 | 2021-10-01 | 四川大学 | High-voltage anti-fatigue potassium-sodium niobate-based lead-free piezoelectric ceramic and preparation method thereof |
| CN113666744A (en) * | 2021-09-17 | 2021-11-19 | 四川大学 | Component gradient potassium sodium niobate based leadless piezoelectric ceramic and preparation method thereof |
| CN114262228A (en) * | 2021-11-26 | 2022-04-01 | 广东奥迪威传感科技股份有限公司 | Potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method and application thereof |
| CN114262228B (en) * | 2021-11-26 | 2024-05-14 | 广东奥迪威传感科技股份有限公司 | Potassium sodium niobate based leadless piezoelectric ceramic and preparation method and application thereof |
| CN114478006A (en) * | 2021-12-31 | 2022-05-13 | 中南大学 | KNNS-BNZ + CuO piezoceramic material and preparation method and application thereof |
| CN116606139A (en) * | 2022-02-08 | 2023-08-18 | 成都理想境界科技有限公司 | Piezoelectric ceramic and preparation method and application thereof |
| CN114621009A (en) * | 2022-03-16 | 2022-06-14 | 南京理工大学 | Lead magnesium niobate-lead titanate-based piezoelectric ceramic material and preparation method thereof |
| CN114621009B (en) * | 2022-03-16 | 2023-02-28 | 南京理工大学 | Lead magnesium niobate-lead titanate-based piezoelectric ceramic material and preparation method thereof |
| CN115093221A (en) * | 2022-07-11 | 2022-09-23 | 广州凯立达电子股份有限公司 | Potassium-sodium niobate-based leadless piezoelectric ceramic sheet, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103482977A (en) | Niobium sodium potassium antimonate-potassium sodium bismuth zirconate leadless piezoelectric ceramic with high piezoelectric constant and preparation method thereof | |
| CN105837210B (en) | Niobium potassium antimonate sodium system leadless piezo-electric ceramic and preparation method thereof | |
| CN100575302C (en) | A kind of ternary system sodium-bismuth titanate lead-free piezoelectric ceramics | |
| CN102531578B (en) | BCT-BZT-BST (Barium calcium titanate-barium zirconate titanate-barium stannate titanate) ternary system lead-free piezoelectric ceramic | |
| CN102757220B (en) | Bi0.5, Na0.5 and TiO3 based ternary-system lead-free piezoelectric ceramic and preparation thereof | |
| CN102180665A (en) | Bismuth scandate-lead titanate high-temperature piezoelectric ceramic material and preparation method thereof | |
| CN109734447B (en) | Lead-free textured ceramic with excellent temperature stability and preparation method thereof | |
| CN102910902B (en) | BNT-BT-BKT-based perovskite system multielement lead-free piezoelectric ceramic and production method thereof | |
| CN109626988B (en) | Piezoelectric ceramic material with high piezoelectric response and high Curie temperature and preparation method thereof | |
| CN105198417B (en) | A kind of preparation method of zirconic acid bismuth sodium lithium cerium dopping potassium-sodium niobate base ceramic material | |
| CN103102154A (en) | Bi0.5Na0.5TiO3-BaTiO3-BiMg0.5Ti0.5O3 lead-free piezoelectric ceramic material | |
| CN107500749A (en) | A kind of laminated structure bismuth piezoelectric ceramic material and preparation method thereof | |
| CN102924078A (en) | BCTZ-based perovskite system multi-component lead-free piezoelectric ceramic and preparation method thereof | |
| CN102167585B (en) | Multielement-doped bismuth titanate group lead-free piezoceramic material and preparation method thereof | |
| CN109796205A (en) | A kind of bismuth laminated titanium bismuth tantalate high temperature piezoceramics and preparation method thereof | |
| CN107244898A (en) | A kind of barium calcium zirconate titanate base leadless piezoelectric ceramics material of barium strontium titanate doping and preparation method thereof | |
| CN101891472B (en) | Perovskite structure high curie temperature leadless piezoelectric ceramal and production method thereof | |
| CN105198411A (en) | Large-strain low-drive electric field relaxation and ferroelectric composite lead-free piezoelectric ceramic and preparation method thereof | |
| CN103288451B (en) | Sodium potassium niobate-sodium bismuth zirconate titanate lead-free piezoelectric ceramic | |
| CN102503409A (en) | Tin calcium barium titanate lead-free piezoelectric ceramic and preparation technology thereof | |
| CN103288450A (en) | Potassium-sodium niobate-bismuth potassium zirconate-titanate/lithium-base leadless piezoelectric ceramic | |
| CN110156459A (en) | One kind being based on BiAlO3Adulterate BaTiO3The preparation method of leadless piezoelectric ceramics energy-storage capacitor | |
| CN102285794B (en) | Lead-free piezoelectric ceramic composed of B-site complex perovskite-structured compounds | |
| CN102336567A (en) | Ternary system high-temperature piezoelectric ceramic of magnesium bismuth titanate, bismuth zinc-based perovskite and lead titanate and preparation method thereof | |
| CN107098701A (en) | Potassium-sodium niobate lithium zirconic acid potassium sodium bismuth scandium acid bismuth ternary series lead-free piezoelectric ceramic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140101 |