CN113880576B - Low sintering temperature and anisotropic strontium barium niobate sodium tungsten bronze type piezoelectric ferroelectric ceramic material and preparation method thereof - Google Patents
Low sintering temperature and anisotropic strontium barium niobate sodium tungsten bronze type piezoelectric ferroelectric ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a strontium barium sodium tungsten bronze niobate piezoelectric ferroelectric ceramic material with low sintering temperature and anisotropy and a preparation method thereof, wherein the general structural formula of the ceramic material is Sr 1.4 Ba 0.6 NaNb 5 O 15 + x wt.% M, wherein M is CuO or MnO 2 And x is 0.25-1.0. The invention modifies Sr through doping Cu and Mn 1.4 Ba 0.6 NaNb 5 O 15 The sintering temperature of the ceramic is greatly reduced, so that the energy consumption of the ceramic in the sintering process is reduced, and the ceramic is energy-saving and environment-friendly; meanwhile, the anisotropy of the ceramic after Cu and Mn doping modification is obviously reduced, the compactness is obviously improved, the electrical property is further improved, the obtained ceramic material has higher dielectric constant and lower dielectric loss, and in addition, the ceramic material has better ferroelectric property. The preparation method is simple, low in cost, good in repeatability and high in yield, and is expected to provide powerful reference for modification research of the tungsten bronze structure lead-free niobate material with the oriented growth.
Description
Technical Field
The invention belongs to the technical field of tungsten bronze structure ceramic materials, and particularly relates to a strontium barium sodium tungsten bronze niobate piezoelectric ferroelectric ceramic material with low sintering temperature and low anisotropy and a preparation method thereof.
Background
With the progress of society and the development of science and technology, materials are continuously intelligentized, integrated and multifunctional, the ferroelectric materials are used as an important dielectric material, the miniaturization and environmental protection requirements of electronic elements are higher, in order to adapt to the production and practical application of the ferroelectric materials, the ferroelectric materials are required to have stable and excellent dielectric and ferroelectric properties, but the current material systems can hardly meet the requirements, and therefore, the development of the ferroelectric materials without lead and with excellent properties is urgent. The tungsten bronze structure lead-free niobate material does not contain lead and other heavy metals, is environment-friendly, can induce flexible and changeable structure and functional characteristics by adjusting the filling condition of crystallographic gaps because octahedral gaps have a series of gap positions with different shapes, can show various performances such as different dielectric, ferroelectric, piezoelectric, pyroelectric, nonlinear optical effects, photoelectric effects and the like along with composition adjustment and structure change, becomes a very important functional material, and is also a key material for research and development of lead-free piezoiron devices. However, since the (001) surface of the tungsten bronze structure compound has lower surface energy and the growth rate thereof is significantly higher than that of other crystal surfaces, the growth rate of the tungsten bronze structure lead-free niobate material in the (001) direction is too fast in the high-temperature sintering process, and anisotropic rod-like grains are easily generated, thereby deteriorating the sintering behavior, reducing the density and further deteriorating the various properties thereof. In view of the above, how to obtain a stable, low temperature sinterable, low anisotropy, and excellent electrical properties piezoelectric ceramic material in a lead-free tungsten bronze system has become a hot problem and is also an urgent need for industrial application.
Disclosure of Invention
The invention aims to provide a strontium barium sodium tungsten niobate piezodielectric ceramic material with low sintering temperature and low anisotropy, and provides a preparation method with simple process, good repeatability and low cost.
Aiming at the purposes, the ceramic material adopted by the invention has the structural general formula of Sr 1.4 Ba 0.6 NaNb 5 O 15 + xwt.% M, wherein x wt.% represents M in Sr 1.4 Ba 0.6 NaNb 5 O 15 X is 0.25 to 1.0; m represents CuO or MnO 2 。
When M represents CuO, x is preferably 0.5.
The preparation method of the strontium barium niobate sodium tungsten bronze piezodielectric ceramic material comprises the following steps:
1. ingredients
According to the general formula Sr 1.4 Ba 0.6 NaNb 5 O 15 Respectively weighing SrCO with the purity of over 98.00 percent 3 、BaCO 3 、Na 2 CO 3 、Nb 2 O 5 Uniformly mixing all the weighed raw materials, putting the mixture into a nylon tank, fully mixing and ball-milling the mixture for 20 to 24 hours by taking zirconium balls as grinding balls and absolute ethyl alcohol as a ball-milling medium, separating the zirconium balls, drying the zirconium balls at the temperature of between 60 and 80 ℃ for 20 to 24 hours, and grinding the mixture by using a mortar to obtain a raw material mixture;
2. pre-firing
Placing the raw material mixture in an alumina crucible, compacting by using an agate rod, covering, placing in a resistance furnace, pre-burning for 5-8 hours at 1210-1250 ℃, naturally cooling to room temperature, and grinding by using a mortar to obtain pre-burning powder;
3. secondary ball mill
Putting the pre-sintered powder and the sintering aid into a nylon tank, taking zirconium balls as grinding balls and absolute ethyl alcohol as a ball-milling medium, fully mixing and ball-milling for 20-24 hours, separating the zirconium balls, drying at 60-80 ℃ for 20-24 hours, and grinding by using a mortar to obtain the pre-sintered powder containing the sintering aid; the sintering aid is CuO or MnO 2 The addition amount of the sintering aid is 0.25-1.0% of the mass of the pre-sintering powder;
4. granulating and tabletting
Adding 5% polyvinyl alcohol aqueous solution by mass into pre-sintering powder containing a sintering aid, granulating, sieving with a 80-120 mesh sieve, and pressing into a cylindrical blank by using a powder tablet press;
5. glue discharging
Placing the cylindrical blank on a zirconium oxide plate, placing the zirconium oxide plate in an alumina closed sagger, heating to 500 ℃ in 380 minutes, preserving heat for 3 hours, and naturally cooling to room temperature along with a furnace to obtain a cylindrical blank after binder removal;
6. pressureless closed sintering
Heating the cylindrical blank body with the glue discharged to 1000 ℃ at the heating rate of 10 ℃/min, heating to 1230-1250 ℃ at the heating rate of 3 ℃/min, preserving the heat for 20-60 min, continuously cooling to 1180-1200 ℃ at the heating rate of 3 ℃/min, preserving the heat for 1-3 h, and naturally cooling to room temperature along with the furnace to obtain the strontium barium sodium tungsten niobate piezodielectric ceramic material; or heating the cylindrical blank with the discharged glue to 1000 ℃ at the heating rate of 10 ℃/minute, heating to 1250-1380 ℃ at the heating rate of 3 ℃/minute, sintering for 3-5 hours, and naturally cooling to room temperature along with the furnace to obtain the strontium niobate barium sodium tungsten bronze piezoelectric ceramic material.
In the step 2, the raw material mixture is preferably calcined at 1230 ℃ for 6 hours, and the temperature rise rate of the calcination is preferably 3 ℃/min.
In the step 3, the sintering aid is preferably CuO, and the addition amount of CuO is 0.5% of the mass of the pre-sintered powder. Preferably, in step 6, the cylindrical blank after glue discharging is heated to 1000 ℃ at a heating rate of 10 ℃/min, then heated to 1230 ℃ at a heating rate of 3 ℃/min, kept at the temperature for 30 min, continuously cooled to 1200 ℃ at a heating rate of 3 ℃/min, kept at the temperature for 2 h, and naturally cooled to room temperature along with the furnace.
The invention has the following beneficial effects:
1. in the invention, sr is selected 1.4 Ba 0.6 NaNb 5 O 15 Adding sintering aid CuO or MnO into the system 2 Sr is modified by doping Cu and Mn 1.4 Ba 0.6 NaNb 5 O 15 Greatly reduce Sr 1.4 Ba 0.6 NaNb 5 O 15 The sintering temperature of the system ceramic is the lowest in the tungsten bronze system ceramic, so that the energy loss of the ceramic in the sintering process is reduced, and the concept of energy conservation and environmental protection is met; meanwhile, cu and Mn are doped with modified Sr 1.4 Ba 0.6 NaNb 5 O 15 The anisotropy of the system ceramic is obviously reduced, the density is obviously improved, and the ceramic material obtains more excellent dielectric and ferroelectric properties.
2. The preparation method is simple, low in cost, good in repeatability and high in yield, and is expected to provide powerful reference for modification research of the tungsten bronze structure lead-free niobate material with the oriented growth.
Drawings
Fig. 1 is an XRD pattern of the strontium barium sodium tungsten niobate bronze type piezodielectric ceramic material prepared in comparative example 1 and examples 1 to 8.
Fig. 2 is a graph showing the anisotropy and bulk density of the strontium barium sodium tungsten niobate piezoelectric ferroelectric bronze material prepared in comparative example 1 and examples 1 to 4.
Fig. 3 is a graph comparing anisotropy and bulk density of the strontium barium niobate sodium tungsten bronze type piezoelectric ferroelectric ceramic material prepared in comparative example 1 and examples 5 to 8.
Fig. 4 is a distribution diagram of grain sizes of the strontium barium niobate sodium tungsten bronze type piezoelectric ferroelectric ceramic material prepared in example 2 along the c-axis and the a/b-axis (the inset is an SEM image of the ceramic sample).
Fig. 5 is a graph of dielectric constant and dielectric loss of the strontium barium niobate sodium tungsten bronze type piezodielectric ceramic material prepared in comparative example 1 at different test frequencies.
Fig. 6 is a graph of dielectric constant and dielectric loss of the strontium barium niobate sodium tungsten bronze type piezoelectric ferroelectric ceramic material prepared in example 2 at different test frequencies.
Fig. 7 is an electrical hysteresis loop diagram of the strontium barium niobate sodium tungsten bronze type piezodielectric ceramic material prepared in comparative example 1 and examples 1 to 8.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
1. Ingredients
According to Sr 1.4 Ba 0.6 NaNb 5 O 15 Respectively weighing SrCO with the purity of 99.00 percent 3 5.9873g BaCO with purity of 99.00% 3 3.4300g Na with 99.80% purity 2 CO 3 1.5229g Nb with 99.99% purity 2 O 5 19.0598g, mixing uniformly, putting into a nylon tank, taking zirconium balls as grinding balls and absolute ethyl alcohol as a ball milling medium, fully mixing and ball milling for 24 hours by adopting a ball mill with the rotation speed of 401 r/min, separating the zirconium balls, drying for 24 hours at 80 ℃, and grinding for 30 minutes by using a mortar to obtain a raw material mixture.
2. Pre-firing
Placing the raw material mixture into an alumina crucible, compacting by an agate rod, covering, placing into a resistance furnace, heating to 1230 ℃ at the heating rate of 3 ℃/minute, preserving the heat for 6 hours, naturally cooling to room temperature along with the furnace, discharging, and grinding for 30 minutes by a mortar to obtain the pre-sintered powder.
3. Secondary ball milling
And (2) filling 20g of pre-sintering powder and 0.05g of CuO with the purity of 99.99% into a nylon tank, taking zirconium balls as grinding balls and absolute ethyl alcohol as a ball milling medium, fully mixing and ball milling for 20 hours by adopting a ball mill with the rotating speed of 401 r/min, separating the zirconium balls, drying for 24 hours in a drying box at the temperature of 80 ℃, and grinding for 30 minutes by using a mortar to obtain the CuO-containing pre-sintering powder.
4. Granulating and tabletting
Adding 5g of 5 mass percent polyvinyl alcohol aqueous solution into 10g of CuO-containing pre-sintered powder, granulating, sieving with a 120-mesh sieve to prepare spherical particles, putting the spherical particles into a stainless steel die with the diameter of 11.5mm, and pressing the spherical particles into a cylindrical blank with the thickness of 1.0mm by using a powder tablet machine under the pressure of 60 MPa.
5. Glue discharging
And (3) placing the cylindrical blank on a zirconium oxide plate, placing the zirconium oxide plate in an alumina closed sagger, heating to 500 ℃ within 380 minutes, preserving the heat for 3 hours, naturally cooling to room temperature along with the furnace, and removing organic matters to obtain the cylindrical blank after rubber removal.
6. Pressureless closed sintering
Heating the cylindrical blank with the discharged glue to 1000 ℃ at the heating rate of 10 ℃/min, heating to 1230 ℃ at the heating rate of 3 ℃/min, preserving the heat for 30 min, continuously cooling to 1200 ℃ at the heating rate of 3 ℃/min, preserving the heat for 2 h, and naturally cooling to room temperature along with the furnace to obtain Sr with the structural formula 1.4 Ba 0.6 NaNb 5 O 15 +0.25wt.% CuO piezoelectric ceramic material of the barium strontium niobate sodium tungsten bronze type.
Example 2
In step 3 of this example, 20g of the pre-fired powder and 0.1g of CuO having a purity of 99.99% were charged into a nylon pot, and the other steps were the same as in example 1 to obtain Sr, a chemical formula of which 1.4 Ba 0.6 NaNb 5 O 15 +0.5wt.% CuO of a barium strontium niobate sodium tungsten bronze type piezodielectric ceramic material.
Example 3
In step 3 of this example, 20g of pre-fired powder and 0.15g of CuO having a purity of 99.99% were charged into a nylon pot; in the step 6, the cylindrical blank body with the discharged glue is heated to 1000 ℃ at the heating rate of 10 ℃/minute, then heated to 1230 ℃ at the heating rate of 3 ℃/minute, is kept warm for 30 minutes, is continuously cooled to 1180 ℃ at the heating rate of 3 ℃/minute, is kept warm for 2 hours, and is naturally cooled to the room temperature along with the furnace, and other steps are the same as the step 1, so that Sr with the structural formula 1.4 Ba 0.6 NaNb 5 O 15 +0.75wt.% CuO of a barium strontium niobate sodium tungsten bronze type piezodielectric ceramic material.
Example 4
In step 3 of this example, 20g of pre-fired powder and 0.2g of CuO having a purity of 99.99% were charged into a nylon pot; in the step 6, the cylindrical blank body with the discharged glue is heated to 1000 ℃ at the heating rate of 10 ℃/minute, then heated to 1230 ℃ at the heating rate of 3 ℃/minute, is kept warm for 30 minutes, is continuously cooled to 1180 ℃ at the heating rate of 3 ℃/minute, is kept warm for 2 hours, and is naturally cooled to the room temperature along with the furnace, and other steps are the same as the step 1, so that Sr with the structural formula 1.4 Ba 0.6 NaNb 5 O 15 +1.0wt.% CuO of a barium strontium niobate sodium tungsten bronze type piezodielectric ceramic material.
Example 5
In step 3 of this example, 20g of the pre-fired powder and 0.05g of MnO of 99.95% purity were added 2 Loading into nylon jar, and performing the same other steps as in example 1 to obtain Sr 1.4 Ba 0.6 NaNb 5 O 15 +0.25wt.％MnO 2 The strontium barium niobate sodium tungsten bronze piezoelectric ferroelectric ceramic material.
Example 6
In step 3 of this example, 20g of the pre-fired powder and 0.1g of MnO of 99.95% purity were added 2 Loading into nylon jar, and performing the same other steps as in example 1 to obtain Sr 1.4 Ba 0.6 NaNb 5 O 15 +0.5wt.％MnO 2 The strontium barium niobate sodium tungsten bronze piezoelectric ferroelectric ceramic material.
Example 7
In step 3 of this example, step 20g of preburnt powder and 0.15g of MnO of 99.95% purity 2 Loading into nylon jar, and performing the same other steps as in example 1 to obtain Sr 1.4 Ba 0.6 NaNb 5 O 15 +0.75wt.％MnO 2 The strontium barium niobate sodium tungsten bronze piezoelectric ferroelectric ceramic material.
Example 8
In step 3 of this example, 20g of the pre-fired powder and 0.2g of MnO of 99.95% purity were added 2 Loading into nylon pot; in the step 6, the cylindrical blank body with the discharged glue is heated to 1000 ℃ at the heating rate of 10 ℃/minute, then heated to 1230 ℃ at the heating rate of 3 ℃/minute, is kept warm for 30 minutes, is continuously cooled to 1180 ℃ at the heating rate of 3 ℃/minute, is kept warm for 2 hours, and is naturally cooled to the room temperature along with the furnace, and other steps are the same as the step 1, so that Sr with the structural formula 1.4 Ba 0.6 NaNb 5 O 15 +1.0wt.％MnO 2 The strontium barium niobate sodium tungsten bronze piezoelectric ferroelectric ceramic material.
Comparative example 1
In step 3 of example 1, cuO was not added; in the step 6, the cylindrical blank body with the glue discharged is heated to 1000 ℃ at the heating rate of 10 ℃/minute, then heated to 1360 ℃ at the heating rate of 3 ℃/minute, kept warm for 4 hours, and naturally cooled to room temperature along with the furnace, and other steps are the same as those in the example 1, so that the strontium barium sodium tungsten niobate piezoelectric ceramic material is obtained.
The strontium barium sodium tungsten bronze niobate piezoelectric ceramic materials prepared in the above examples 1 to 8 and the strontium barium sodium tungsten bronze niobate piezoelectric ceramic material prepared in the comparative example 1 were polished, ultrasonically treated, and wiped clean, and silver pastes were respectively coated on the upper and lower surfaces thereof, and were placed in a muffle furnace at 840 ℃ for 30 minutes, and naturally cooled to room temperature. Carrying out structural characterization by adopting a SmartLab9 type ray diffractometer produced by Japan science company; performing micro-morphology characterization by using an SU3500 tungsten filament scanning electron microscope produced by Hitachi high and New company, collecting the grain sizes of c axis and a/b axis of ceramic grains by using Nano Measurer software, and measuring the bulk density of the ceramic by using Archimedes principle; the electrical properties of 4294A, E4980A dielectric analyzer manufactured by Agilent technologies, inc. and a ferroelectric tester manufactured by Radiant, USA are tested, and related morphology and performance parameters are calculated according to the following formula:
anisotropy f l ：f l ＝d c /d a/b
Bulk density ρ b ：ρ b ＝m 1 (ρ 0 -ρ l )/(m 1 -m 2 )+ρ l
Dielectric constant ε r ：ε r ＝4Ct/(πε 0 d)
In the formula: d is a radical of c Average grain size of ceramic grains along the c-axis, d a/b Is the average grain size of the ceramic grains along the a/b axis, m 1 Mass m of the ceramic sample in air 2 Is the wet weight, rho, of the ceramic sample in distilled water l Is the density of air (0.0012 g/cm) 3 )，ρ 0 Is the density of distilled water at the test temperature, C is the capacitance, t is the thickness of the ceramic sample, ε 0 The dielectric constant is 8.85X 10 -12 F/m), d is the diameter of the ceramic sample. The results are shown in FIGS. 1 to 7 and Table 1.
TABLE 1 Properties of piezoelectric ceramic materials of comparative example 1 and examples 1 to 8
As can be seen from FIG. 1, small amounts of Na are present in the ceramic materials prepared in examples 3 and 4 0.5 Sr 0.25 NbO 3 The second phase, the ceramic materials prepared in the other examples and comparative examples, formed pure Tetragonal Tungsten Bronze (TTB) with no other miscellaneous peaks found. As can be seen from FIGS. 2 and 3 and Table 1, the ceramic material prepared in comparative example 1 had a sintering temperature of 1360 deg.C, an anisotropy of 2.725, and a bulk density of 4.808g/cm 3 By adding the sintering aid, the sintering temperature and the anisotropy of the ceramic materials prepared in the examples 1 to 8 are both obviously reduced, the bulk density is obviously increased, the sintering temperature is about 1180 ℃ to 1200 ℃, the anisotropy is about 1.791 to 2.465, and the bulk density is about 5.009 to 5.036g/cm 3 In particularWhen the sintering aid is CuO and the addition amount of the sintering aid is 0.5wt.%, the anisotropy of the ceramic is as low as 1.791, and the bulk density is as high as 5.036g/cm 3 . As can be seen from FIG. 4, the average grain size of the ceramic material prepared in example 2 along the a/b axis is 1.6 μm, the average grain size along the c axis is 2.8 μm, the difference between the two is small, the ceramic growth gradually tends to be isotropic, and the ceramic sample presents a denser microstructure. As can be seen from FIGS. 5 to 7 and Table 1, the ceramic materials prepared in examples 1 to 8 had lower dielectric loss (tan. Delta.) and lower remanent polarization (P) than those of comparative example 1 r ) Higher and the ceramic material prepared in example 2 has a higher dielectric constant than that of comparative example 1, which fully indicates that the introduction of appropriate amounts of Cu and Mn improves the electrical properties of the strontium barium niobate sodium tungsten bronze type piezoelectirc material, especially when the sintering aid is CuO, added in an amount of 0.5wt.%, the dielectric constant of the ceramic material is improved from 973.6 of comparative example 1 to 991.0, the dielectric loss is reduced from 0.044 of comparative example 1 to 0.027, and the remanent polarization is improved from 6.791 of comparative example 1 to 8.620.
Claims (4)
1. A kind of low sintering temperature and anisotropic strontium barium niobate sodium tungsten bronze type piezoelectricity ferroelectric ceramic material, characterized by that: the structural general formula of the ceramic material is Sr 1.4 Ba 0.6 NaNb 5 O 15 +xwt.% M, whereinxwt.% of M in Sr 1.4 Ba 0.6 NaNb 5 O 15 The mass percentage of (A) to (B),xthe value of (A) is 0.25-1.0; m represents CuO or MnO 2 ；
The preparation method of the ceramic material comprises the following steps:
(1) Ingredients
According to the general formula Sr 1.4 Ba 0.6 NaNb 5 O 15 Respectively weighing SrCO with the purity of over 98.00 percent 3 、BaCO 3 、Na 2 CO 3 、Nb 2 O 5 Mixing all the materials, loading into nylon tank, mixing zirconium balls as grinding balls and absolute alcohol as ball grinding medium, ball grinding for 20-24 hr, separating zirconium balls, drying at 60-80 deg.c for 20-24 hr, and grinding in mortarGrinding to obtain a raw material mixture;
(2) Pre-firing
Placing the raw material mixture in an alumina crucible, compacting by using an agate rod, covering, placing in a resistance furnace, pre-burning for 5-8 hours at 1210-1250 ℃, naturally cooling to room temperature, and grinding by using a mortar to obtain pre-burning powder;
(3) Secondary ball milling
Putting the pre-sintered powder and the sintering aid into a nylon tank, taking zirconium balls as grinding balls and absolute ethyl alcohol as a ball-milling medium, fully mixing and ball-milling for 20-24 hours, separating the zirconium balls, drying at 60-80 ℃ for 20-24 hours, and grinding by using a mortar to obtain the pre-sintered powder containing the sintering aid; the sintering aid is CuO or MnO 2 The addition amount of the sintering aid is 0.25-1.0% of the mass of the pre-sintered powder;
(4) Granulating and tabletting
Adding 5% polyvinyl alcohol aqueous solution by mass into pre-sintering powder containing a sintering aid, granulating, sieving with a 80-120 mesh sieve, and pressing into a cylindrical blank by using a powder tablet press;
(5) Glue discharging
Placing the cylindrical blank on a zirconium oxide plate, placing the zirconium oxide plate in an alumina closed sagger, heating to 500 ℃ within 380 minutes, preserving heat for 3 hours, and naturally cooling to room temperature along with a furnace to obtain a cylindrical blank after glue removal;
(6) Pressureless closed sintering
Heating the cylindrical blank with the glue discharged to 1000 ℃ at the heating rate of 10 ℃/min, heating to 1230-1250 ℃ at the heating rate of 3 ℃/min, preserving the heat for 20-60 min, continuously cooling to 1180-1200 ℃ at the heating rate of 3 ℃/min, preserving the heat for 1-3 h, and naturally cooling to room temperature along with the furnace to obtain the strontium barium sodium tungsten niobate piezoelectric ceramic material;
or heating the cylindrical blank with the discharged glue to 1000 ℃ at the heating rate of 10 ℃/minute, heating to 1250-1380 ℃ at the heating rate of 3 ℃/minute, sintering for 3-5 hours, and naturally cooling to room temperature along with the furnace to obtain the strontium niobate barium sodium tungsten bronze piezoelectric ceramic material.
2. The low sintering temperature and anisotropic strontium barium niobate sodium tungsten bronze type piezoferroelectric ceramic material of claim 1, characterized in that: said M represents a CuO,xthe value of (2) is 0.5, the sintering aid is CuO, and the addition amount of the CuO is 0.5 percent of the mass of the pre-sintering powder.
3. The low sintering temperature and anisotropic strontium barium niobate sodium tungsten bronze type piezoferroelectric ceramic material of claim 1, characterized in that: in the step (2), the pre-sintering is carried out for 6 hours at 1230 ℃, and the temperature rise rate of the pre-sintering is 3 ℃/minute.
4. The low sintering temperature and anisotropic strontium barium niobate sodium tungsten bronze type piezoferroelectric ceramic material of claim 1, characterized in that: in the step (6), the cylindrical blank body with the discharged glue is heated to 1000 ℃ at the heating rate of 10 ℃/minute, then heated to 1230 ℃ at the heating rate of 3 ℃/minute, kept at the temperature for 30 minutes, continuously cooled to 1200 ℃ at the heating rate of 3 ℃/minute, kept at the temperature for 2 hours, and naturally cooled to room temperature along with the furnace.
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| CN101160269A (en) * | 2005-04-18 | 2008-04-09 | 株式会社村田制作所 | Dielectric ceramic composition and monolithic ceramic capacitor |
| CN103172374A (en) * | 2011-12-26 | 2013-06-26 | Tdk株式会社 | Piezoelectric ceramic and piezoelectric device |
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| CN101160269A (en) * | 2005-04-18 | 2008-04-09 | 株式会社村田制作所 | Dielectric ceramic composition and monolithic ceramic capacitor |
| CN103172374A (en) * | 2011-12-26 | 2013-06-26 | Tdk株式会社 | Piezoelectric ceramic and piezoelectric device |
| CN105541413A (en) * | 2016-02-03 | 2016-05-04 | 陕西师范大学 | High-d33 lead-free strontium calcium niobate sodium tungsten bronze piezo-ferroelectric ceramic material and preparation method thereof |
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