CN114605146A - BaTiO with large room-temperature electrostrictive strain3Base leadless piezoelectric ceramic and preparation method thereof - Google Patents

BaTiO with large room-temperature electrostrictive strain3Base leadless piezoelectric ceramic and preparation method thereof Download PDF

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CN114605146A
CN114605146A CN202210275000.7A CN202210275000A CN114605146A CN 114605146 A CN114605146 A CN 114605146A CN 202210275000 A CN202210275000 A CN 202210275000A CN 114605146 A CN114605146 A CN 114605146A
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李彩霞
王婉茹
刘一帆
王泽宇
李晶
赵艺雯
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Harbin University of Science and Technology
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Abstract

BaTiO with large room-temperature electrostrictive strain3A lead-free piezoelectric ceramic and a preparation method thereof relate to a piezoelectric ceramic and a preparation method thereof. Aims to solve the problem of the prior BaTiO3The problems of small electric strain and high sintering temperature of the base lead-free piezoelectric ceramic at room temperature are solved. The chemical formula of the piezoelectric ceramic is Ba0.70Ca0.30TiO3+x mol％MnO2. The method comprises the following steps: firstly, weighing raw material powder according to a stoichiometric ratio; secondly, mixing, ball-milling, drying and pressing the raw materials into an embryo body to be pre-sintered; pre-burning the blank to be pre-burned, crushing, ball-milling again, mixing with polyvinyl alcohol adhesive, granulating, pressing into a thin cylindrical blank, removing adhesive, sintering into porcelain, and cooling along with a furnace to obtain a ceramic blank; fourthly, annealing and polishing the ceramic blank body to obtain the BaTiO with large room temperature electrostriction3A lead-free piezoelectric ceramic. The invention is applied to the field of piezoelectric materials.

Description

BaTiO with large room-temperature electrostrictive strain3Base leadless piezoelectric ceramic and preparation method thereof
Technical Field
The invention relates to a lead-free piezoelectric ceramic and a preparation method thereof.
Background
Based on the strong demand of the electronic material market for environment-friendly materials and the development trend of integration, multifunctionalization and high frequency of electronic components, the method has no defectsThe electrical properties of lead piezoelectric materials face more stringent challenges and requirements during application. Especially, a piezoelectric actuator with large driving force or large displacement is strongly eager for a piezoelectric material with large electrostrictive strain effect, and in addition, based on the requirements of environmental protection and health, the research and development of environment-friendly piezoelectric ceramics with large electrostrictive strain is of great significance for the practicability of lead-free materials. In recent years, a series of high-performance environment-friendly electrostrictive materials, such as BaTiO, have been developed3Base ceramic, Bi0.5Na0.5TiO3Base material (mainly including ceramic, textured ceramic and single crystal) and K0.5Na0.5NbO3A base ceramic. Wherein, Bi0.5Na0.5TiO3The base piezoelectric ceramic becomes one of hotspot materials concerned by researchers through large room-temperature electrostriction, good temperature stability and simple preparation process, and has great potential in the application aspect of piezoelectric actuators, but Bi contained in the base piezoelectric ceramic is toxic and extremely volatile in the high-temperature sintering process, and is also harmful to the environment and human health, the high-temperature volatilization of Bi cannot ensure the stoichiometric ratio of a sintered ceramic sample, the coercive field of the base piezoelectric ceramic is large, and the base piezoelectric ceramic is difficult to polarize sufficiently, and the defects prevent the application and the sufficient release of piezoelectric performance of the base piezoelectric ceramic; and BaTiO3Because of its high sintering temperature (usually higher than 1350 ℃), its working temp. range is narrow (Curie temp. T)CTypically below 120 c), especially lower electrostrictive strains do not dominate in piezoelectric actuator applications. Researchers construct BaTiO through component design3Research on BaTiO through multiple methods such as Morphotropic Phase Boundary (MPB) based on binary or multi-element solid solution, ion doping, sintering aid adding, preparation process changing (raw material controlling, preparation method changing, sintering atmosphere changing, pre-sintering and sintering process parameter controlling), polarization condition optimizing and heat treatment (annealing or quenching), and the like3Regulating and controlling the structure and the electrical property of the base ceramic; on the other hand, the lower melting point additive is introduced into BaTiO3The base ceramic can also be used as a sintering aid in the preparation process, the sintering temperature of the base ceramic is effectively reduced to below 1300 ℃, and BaTiO3The base ceramic has no volatile element and toxic element and has excellent chemical stability, so that the BaTiO with large electrostrictive effect3The research of the lead-free piezoelectric ceramic has important significance for realizing the practicability of environment-friendly materials of the piezoelectric actuator.
Disclosure of Invention
The invention aims to solve the problem of the existing BaTiO3The problems of weak room-temperature electrostriction and high sintering temperature of the base lead-free piezoelectric ceramic are solved, and the BaTiO with large room-temperature electrostriction is provided3A lead-free piezoelectric ceramic and a preparation method thereof.
The invention relates to BaTiO with large room temperature electrostriction3The chemical formula of the lead-free piezoelectric ceramic is Ba0.70Ca0.30TiO3+x mol％MnO2Wherein x is a mole fraction, and x is more than or equal to 0.55 and less than or equal to 0.65.
The BaTiO with large room temperature electrostriction3The preparation method of the base lead-free piezoelectric ceramic comprises the following steps:
firstly, mixing the raw material BaCO3、CaCO3、TiO2And MnO2According to the formula Ba0.70Ca0.30TiO3+x mol％MnO2Wherein x is more than or equal to 0.55 and less than or equal to 0.65;
secondly, mixing the powder weighed in the first step with absolute ethyl alcohol, putting the mixture into a ball milling tank, ball milling the mixture for 22-24 hours by using a planetary ball mill at the rotating speed of 150-200 revolutions/min, taking out the slurry, putting the slurry into a drying oven at 90 ℃, keeping the temperature for 4 hours, drying the slurry, and keeping the slurry for 1-2 minutes at 10-16 MPa by using a tablet press to obtain a cylindrical blank to be presintered, wherein the cylindrical blank to be presintered has the diameter of 55-60 mm and the thickness of 4-6 mm; wherein the ratio of the mass of the absolute ethyl alcohol to the total mass of the powder is (1.2-1.6): 1; the grinding balls used for ball milling are composed of agate balls with the diameters of 20mm, 10mm and 6mm respectively according to the number ratio of 1:10: 15;
thirdly, putting the blank to be presintered obtained in the second step into a muffle furnace, heating to 900-950 ℃ at the heating rate of 2-3 ℃/min, preserving heat for 2-4 h, and cooling along with the furnace to obtain a presintered tablet;
fourthly, crushing the pre-sintered tablets to 70-130 meshes of powder, adding absolute ethyl alcohol to mix into a solution, ball-milling the solution in a ball-milling tank at the rotating speed of 150-200 revolutions per minute for 22-24 hours by using a planetary ball mill, keeping the temperature for 4 hours at 90 ℃, drying the slurry, adding 7 wt% of polyvinyl alcohol solution adhesive into powder, adding 1-1.5 drops of adhesive into 1g of powder on average, placing the powder in the air for 22-24 hours, granulating, sieving the powder by using a 100-mesh sieve and a 150-mesh sieve, taking 150 meshes of powder, maintaining the pressure for 1-3 minutes at 5-7 MPa by using a tablet press to obtain a thin wafer blank with the diameter of 9-11 mm and the thickness of 0.5-1.0 mm, stacking the blank up and down, burying the blank with the same components of powder, increasing the temperature to 600 ℃ at the rate of 2-4 ℃/min in a muffle furnace, keeping the temperature for 2 hours, discharging the adhesive, cooling along with the furnace, then putting the blank into the muffle furnace again, and sintering the blank in a step-type temperature increasing mode, namely increasing the temperature to 800 ℃ at the rate of 2-4 ℃/min, heating to 1230-1340 ℃ at the heating rate of 1.5-2 ℃/min, keeping the temperature for 3-4 h, sintering, and cooling to room temperature along with the furnace to obtain a ceramic blank; in the fourth step, the mass ratio of the absolute ethyl alcohol to the powder pre-sintered and pressed is (1.2-1.6): 1.
Fifthly, embedding the ceramic blank into powder with the same components, heating to 800 ℃ at a heating rate of 1.5-3 ℃/min, keeping the temperature in the air for 4-6 h for annealing, cooling to room temperature along with the furnace, adding deionized water into corundum powder, and polishing a sample on a smooth glass plate to obtain the BaTiO with large electrostrictive strain at room temperature3A base lead-free piezoelectric ceramic;
the invention has the advantages that:
1. the invention adopts the coexisting Ba of ferroelectric tetragonal phase-dielectric orthorhombic phase at room temperature0.70Ca0.30TiO3Introduction of polyvalent ions Mn (Mn) into ceramic matrix2+，Mn3+And Mn4+) MnO with lower melting point (-535 ℃) for carrying out B-site acceptor doping2At Ba0.70Ca0.30TiO3The ceramic sample is used as a sintering aid in the ceramic sintering process to reduce the sintering temperature of the sample by 110 ℃, and the prepared ceramic sample has a perovskite structure with coexisting tetragonal-orthogonal two phases along with MnO2The doping amount is increased, the average grain size of the ceramic sample is increased firstly and then reduced, the density is improved, and the unit cell volume is increased;
2. BaTiO of the invention3The lead-free piezoelectric ceramic has larger bilateral electrostriction bipolar SmaxUnilateral electrostrictive Unipolar SmaxAnd inverse piezoelectric coefficient
Figure BDA0003555503350000031
(
Figure BDA0003555503350000032
Wherein SmaxIs unilateral maximum electrical strain, EmaxThe maximum electric field applied in the single-sided strain curve). Ba of the invention is measured in an external alternating current field of 50kV/cm at 10Hz at room temperature0.70Ca0.30TiO3+0.6mol％MnO2Bilateral electrostrictive bipolar S of ceramicsmaxUnilateral electrostrictive Unipolar SmaxAnd inverse piezoelectric coefficient
Figure BDA0003555503350000033
The maximum values are 0.56%, 0.75% and 1500pm/V respectively, and the large electric strain is even higher than Bi reported in the literature at present0.5Na0.5TiO3Base materials and commercial PZT ceramics;
3. BaTiO prepared by the invention3The lead-free piezoelectric ceramic has good room temperature dielectric, ferroelectric, electrostrictive strain and piezoelectric properties, and the optimal comprehensive room temperature electrical property parameter is the relative dielectric constant epsilonr1323, dielectric loss tangent tan δ 0.08, TC66 ℃ maximum of polarization Pmax＝12.2μC/cm2Residual polarization Pr＝6.9μC/cm2Coercive field EC13.3kV/cm, piezoelectric constant d33116pC/N, planar electromechanical coupling coefficient kp0.22%, mechanical quality factor Qm684 inverse piezoelectric coefficient
Figure BDA0003555503350000034
Figure BDA0003555503350000035
The change of Mn doping quantity has obvious influence on the unit cell structure, microstructure, dielectric, ferroelectric, electric strain and piezoelectric performance, and the electric strain shows good component stability in the range of x being 0.55-0.65.
4. BaTiO obtained by the invention3The lead-free piezoelectric ceramic material has simple preparation process, no volatile elements, no toxic substances,the piezoelectric actuator has the advantages of environmental protection, sintering temperature lower than 1300 ℃, low cost, easily controlled process, convenience for industrial production, lower driving electric field, hopeful satisfaction of industrial requirements, and huge application potential in the application aspect of piezoelectric actuators with large driving force or large displacement.
Drawings
FIG. 1 shows Ba prepared according to a sixth embodiment0.70Ca0.30TiO3+x mol％MnO2Powder X-ray diffraction pattern (XRD) of ceramic (X ═ 0 to 0.7); FIG. 2 illustrates the preparation of Ba according to the sixth embodiment0.70Ca0.30TiO3+x mol％MnO2Surface back-scattered Scanning Electron Micrographs (SEM) of ceramic samples (x ═ 0,0.2,0.4,0.5,0.55,0.6,0.65 and 0.7); FIG. 3 Ba preparation according to the sixth embodiment0.70Ca0.30TiO3+x mol％MnO2Room temperature hysteresis loops for ceramic samples (x ═ 0,0.2,0.4,0.5,0.55,0.6,0.65, and 0.7); FIG. 4 is a Ba preparation process according to an embodiment0.70Ca0.30TiO3+x mol％MnO2Room temperature ferroelectric property parameter P of ceramic samplemax、PrAnd ECWith MnO2The variation relation curve of the doping amount; FIG. 5 shows Ba prepared according to a sixth embodiment0.70Ca0.30TiO3+x mol％MnO2Bilateral electrical strain curves for ceramic samples (x ═ 0,0.2,0.4,0.5,0.55,0.6,0.65, and 0.7); FIG. 6 shows Ba prepared according to sixth embodiment0.70Ca0.30TiO3+x mol％MnO2Maximum positive strain S on both sides of ceramic samplemaxTotal strain and negative strain SnegWith MnO2The variation relation curve of the doping amount; FIG. 7 shows Ba prepared according to sixth embodiment0.70Ca0.30TiO3+x mol％MnO2Single-sided electrostrictive strain curves of ceramic samples; FIG. 8 shows Ba prepared according to sixth embodiment0.70Ca0.30TiO3+x mol％MnO2Unilateral maximum electrostriction Unipolar S of ceramic samplesmaxAnd inverse piezoelectric coefficient
Figure BDA0003555503350000041
With followingMnO2The variation relation curve of the doping amount; FIG. 9 is Ba prepared in accordance with sixth embodiment0.70Ca0.30TiO3+x mol％MnO2Curie temperature T of ceramic sampleCWith MnO2The variation relation graph of the doping amount.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: BaTiO with large room temperature electrostriction in the embodiment3The chemical formula of the lead-free piezoelectric ceramic is Ba0.70Ca0.30TiO3+x mol％MnO2Wherein x is a mole fraction, and x is more than or equal to 0.55 and less than or equal to 0.65.
The second embodiment is as follows: BaTiO with large room temperature electrostriction in the embodiment3The preparation method of the base lead-free piezoelectric ceramic comprises the following steps:
firstly, mixing the raw material BaCO3、CaCO3、TiO2And MnO2According to the formula Ba0.70Ca0.30TiO3+x mol％MnO2Wherein x is more than or equal to 0.55 and less than or equal to 0.65;
mixing the raw materials weighed in the step one with absolute ethyl alcohol, ball-milling the mixture for 22-24 hours by using a planetary ball mill at the rotating speed of 150-200 revolutions/min, preserving heat at 90 ℃ for 2-4 hours, drying slurry, and maintaining the pressure at 10-16 MPa for 1-2 minutes to obtain a blank to be presintered with the diameter of 55-60 mm and the thickness of 4-6 mm; wherein the ratio of the mass of the absolute ethyl alcohol to the total mass of the raw materials is (1.2-1.6): 1; the grinding balls used for ball milling are composed of agate balls with the diameters of 20mm, 10mm and 6mm respectively according to the number ratio of 1:10: 15;
thirdly, raising the temperature of the blank to be presintered prepared in the second step to 900-950 ℃ at the heating rate of 2-3 ℃/min, and keeping the temperature for 2-4 hours to obtain a presintered tablet;
fourthly, crushing the pre-sintered tablets to 70-130 meshes of powder, mixing the powder with absolute ethyl alcohol, putting the powder into a ball milling tank, ball milling the powder for 22-24 hours by using a planetary ball mill at the rotating speed of 150-200 revolutions per minute, adding 7 wt% of polyvinyl alcohol solution adhesive into dried slurry powder, adding 1-1.5 drops of adhesive into 1g of powder on average, placing the powder in the air for 22-24 hours, granulating, sieving the powder by using a 100-mesh sieve and a 150-mesh sieve, taking 150-mesh powder, maintaining the pressure for 1-3 minutes at 5-7 MPa to obtain a thin wafer blank to be sintered with the diameter of 9-11 mm and the thickness of 0.5-1.0 mm, stacking the blank up and down, burying the blank with the same components of 100 meshes of powder, putting the blank into a muffle furnace, heating to 600 ℃, keeping the temperature for 2 hours, removing the adhesive, cooling the blank along with the furnace, then putting the blank into the muffle furnace again, sintering in a step-type heating manner, heating, namely heating to 800 ℃ at the heating rate of 2-4 ℃/min, keeping the temperature for 2 hours, then heating the blank in the air for 3-4 hours at the heating rate of 1.5-2 ℃/min, cooling to room temperature along with the furnace to obtain a ceramic blank. In the fourth step, the mass ratio of the absolute ethyl alcohol to the powder pre-sintered and pressed into tablets is (1.2-1.6): 1;
fifthly, embedding the ceramic blank into powder with the same components, raising the temperature to 800 ℃ at the heating rate of 1.5-3 ℃/min, keeping the temperature in the air atmosphere for 4-6 h for annealing, cooling to room temperature along with the furnace, adding deionized water into corundum powder, and polishing the ceramic sample on smooth flat glass to obtain the BaTiO with large electrostrictive strain at room temperature3A base lead-free piezoelectric ceramic;
the third concrete implementation mode: the second embodiment is different from the first embodiment in that: in step one, x is 0.6. The rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the first or second embodiment in that: in the third step, the heating rate of the blank to be presintered is 1.5-3 ℃/min, and the presintering condition is 950 ℃ for heat preservation for 4 h. The others are the same as in the second or third embodiment.
The fifth concrete implementation mode: this embodiment is different from one of the third to fourth embodiments in that: in the fourth step, the sintering parameter is 1250 ℃ and the temperature is kept for 4 hours. The other is the same as one of the third to fourth embodiments.
The sixth specific implementation mode: this embodiment is a BaTiO with large electrostrictive strain at room temperature3The preparation method of the base lead-free piezoelectric ceramic comprises the following steps:
firstly, mixing the raw material BaCO3、CaCO3、TiO2And MnO2Push Ba0.70Ca0.30TiO3+x mol％MnO2Stoichiometric weighing of chemical formula, wherein x is 0.6;
secondly, putting the powdery raw materials weighed in the step one into a ball milling tank, adding absolute ethyl alcohol, ball milling for 24 hours at the rotating speed of 170 revolutions per minute, keeping the temperature at 90 ℃ for 4 hours, drying the slurry, and keeping the pressure at 15MPa for 1 minute to obtain a blank to be pre-sintered, wherein the diameter of the blank is 60mm, and the thickness of the blank is 3 mm; wherein the ratio of the mass of the absolute ethyl alcohol to the total mass of the raw materials is 1.3: 1; the grinding balls used for ball milling are composed of agate balls with the diameters of 20mm, 10mm and 6mm according to the number ratio of 1:10: 15;
thirdly, placing the blank to be presintered prepared in the second step into a crucible muffle furnace, heating to 950 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 4 hours to obtain a presintered tablet;
fourthly, crushing the pre-sintered pressed sheet into 150-mesh powder, adding absolute ethyl alcohol, putting the powder into a ball milling tank, ball milling the powder for 24 hours at a rotating speed of 170 revolutions per minute by using a planetary ball mill, taking out slurry, keeping the temperature for 3 hours at 90 ℃, drying the powder, adding 7 wt% of polyvinyl alcohol solution adhesive, adding 2 drops of adhesive into every 1g of powder on average, placing the powder in the air for 24 hours, sieving the powder for granulation, stacking the powder up and down, sieving the powder with 100-mesh and 150-mesh sieves, taking 150-mesh powder, maintaining the pressure for 1 minute at 6MPa to obtain a to-be-sintered blank with the diameter of 10mm and the thickness of 0.6-1 mm, stacking the to-be-sintered blank, burying the to-be-sintered blank with the same components of the powder, heating the blank to 600 ℃ by using a muffle furnace, keeping the temperature for 2 hours, removing the adhesive, cooling the blank along with the furnace, putting the blank into the muffle furnace, keeping the temperature for 2 hours at a step-type heating rate of 2 ℃/min, heating the blank to 800 ℃ for keeping the temperature for 2 hours, heating the atmosphere at a temperature of 1230-1270 ℃ at a heating rate of 1.5-2 ℃/min, keeping the temperature for 3-4 hours, cooling to room temperature along with the furnace to obtain a ceramic blank;
fifthly, heating the ceramic blank to 850 ℃ at a heating rate of 1.5 ℃/min, carrying out heat preservation in air for 4h annealing, cooling to room temperature along with the furnace, and polishing to obtain a ceramic sample, namely the BaTiO with large electrostriction at room temperature3A base lead-free piezoelectric ceramic; in the fourth step, the mass ratio of the absolute ethyl alcohol to the pre-sintered and pressed powder is (1.2-1.6): 1.
In addition, the chemical formula Ba0.70Ca0.30TiO3+x mol％MnO2Wherein x is 0,0.2,0.4,0.5,0.55 and 0.65, respectively, and the experiment was performed according to the method of the present embodiment.
This embodiment prepares a room temperature, large electrostrictive Ba0.70Ca0.30TiO3+x mol％MnO2The room temperature XRD pattern of the ceramic sample is shown in fig. 1, and a single peak (121) near 33 ° 2 θ and a (002)/(200) cleavage peak near 45 ° 2 θ indicate Ba0.70Ca0.30TiO3+x mol％MnO2(x is more than or equal to 0 and less than or equal to 0.7) the ceramic samples all have a composite perovskite crystal structure with coexisting ferroelectric tetragonal phase and dielectric orthorhombic phase along with MnO2The doping amount is increased, Mn replaces Ti at B site4+Resulting in a volume expansion of the unit cell and a compression of the tetragonal phase structure.
Chemical formula Ba0.70Ca0.30TiO3+x mol％MnO2(x ═ 0-0.7) surface back-scattered SEM photographs of the ceramic samples are shown in fig. 2; illustrating Ba prepared in this embodiment0.70Ca0.30TiO3+x mol％MnO2The ceramic samples have good crystallization, clear crystal grains and crystal boundaries, compact structure but uneven grain size distribution, and all the samples comprise two kinds of crystal grains with different sizes, namely, some orthorhombic (black) small crystal grains are surrounded by tetragonal (white) larger crystal grains and are consistent with the complex phase structure characteristics of the samples in XRD test results. The average grain size distribution is obviously influenced by the doping amount, and the average grain sizes of the orthorhombic phase and the tetragonal phase are changed along with MnO2The increase of the doping amount increases first and then decreases, and the average grain size of the sample is largest at 0.6 of the composition x in the present embodiment.
Ba is mixed with0.70Ca0.30TiO3+x mol％MnO2Polishing the upper and lower surfaces of a ceramic sample on a smooth glass plate by using corundum powder and deionized water, coating silver paste, keeping the temperature at 600 ℃ for 1h, firing to form full electrodes, wherein the size of each electrode is 10-13 mm, and measuring different MnO contents by using a TD-88A ferroelectric comprehensive tester under an alternating current field of 10Hz and 50kV/cm at room temperature2The electrical hysteresis loop, the bilateral electrostrictive strain curve and the unilateral electrostrictive strain curve of the doped ceramic sample. Ba0.70Ca0.30TiO3+x mol％MnO2The room temperature hysteresis loop of the (x-0-0.7) ceramic sample is shown in fig. 3, and the corresponding room temperature ferroelectric property parameter is dependent on MnO2Variation of doping amountThe relationship is shown in FIG. 4, from which it can be seen that MnO2The increase of the doping amount enables the electric hysteresis loop of the sample to gradually become high and fat, and the corresponding maximum value P of the polarization intensitymaxRemanent polarization PrAnd coercive field ECAll increase and decrease first, excessive MnO2Doping makes the electric hysteresis loop become flat, and the best room temperature ferroelectric property P is obtained at the position where the component x is 0.6 in the embodimentr＝6.87μC/cm2，EC＝13.35kV/cm。
The Ba prepared by the embodiment is tested by adopting a TD-88A ferroelectric comprehensive tester0.70Ca0.30TiO3+x mol％MnO2(x ═ 0,0.2,0.4,0.5,0.55,0.6,0.65, and 0.7) room temperature bilateral electrical strain loops for the ceramics are shown in fig. 5, and it can be seen that all samples exhibit a typical butterfly curve, and the asymmetry of the bilateral electrical strain curve arises from the built-in electric field E formed in the sample by doping the B-site Mn acceptoriFunction of (1), i.e. acceptor ion Mn (Mn)2+,Mn3+,Mn4+) Substituted Ba0.70Ca0.30TiO3B site Ti of4+Oxygen vacancy defects are caused, oxygen vacancy defects and acceptor cations form defect dipoles, the defect dipoles are arranged in parallel to the spontaneous polarization direction under the action of an external electric field, and a built-in electric field E oriented along the spontaneous polarization is formediThe strain of the forward electric field of the sample is larger, and the bilateral electrostriction curve is asymmetric. The Mn doping amount is increased to ensure the maximum positive strain S on both sides of the ceramicmaxTotal strain and negative strain SnegAll of which are increased and then decreased, as shown in fig. 6, the component x of the present embodiment is bilateral strain S in 50kV/cm ac electric field at 0.6maxA maximum of 0.56% is reached, S is found at x ═ 0.55 and x ═ 0.65maxAlso up to 0.55% and 0.50%, respectively, of BaTiO prepared according to the invention3The base lead-free ceramic sample showed good stability of the large electrostrictive component at room temperature.
The Ba prepared by the embodiment is tested at 50kV/cm and 10Hz by a TD-88A ferroelectric comprehensive tester0.70Ca0.30TiO3+x mol％MnO2(x ═ 0,0.2,0.4,0.5,0.55,0.6,0.65, and 0.7) room temperature single-sided electrostrictive curves for ceramic samples, e.g.As shown in fig. 7. As can be seen, Ba0.70Ca0.30TiO3MnO in ceramics2Increase of doping amount to unilateral strain Unipolar S of samplemaxThe regulation effect is very obvious, the unilateral strain is increased and then reduced, the strain reaches the maximum value of 0.75 percent at the x-0.6 component, and the corresponding inverse piezoelectric coefficient
Figure BDA0003555503350000071
Up to 1500 pm/V. Unilateral strain Unipolar S of ceramic samplesmaxAnd inverse piezoelectric coefficient
Figure BDA0003555503350000083
The composition-dependent relationship is shown in fig. 8, the unilateral strains at x ═ 0.55 and x ═ 0.65 are 0.69% and 0.53%, respectively,
Figure BDA0003555503350000084
1384pm/V and 1050pm/V, respectively, of the BaTiO produced in this embodiment3The lead-free piezoelectric ceramic shows good stability of electrostrictive components, and the large electrostrictive effect of the lead-free piezoelectric ceramic is even superior to that of the prior commercial PZT ceramic and Bi reported in literature0.5Na0.5TiO3The ceramic base is favorable for being applied to a piezoelectric actuator with large driving force or large displacement.
An Agilent 4284A type impedance analyzer and a temperature control device are adopted to collect Ba prepared by the embodiment in a temperature range of-80-200 DEG C0.70Ca0.30TiO3+x mol％MnO2Relative dielectric constant ε of ceramic sample at 1kHzrObtaining Curie temperature T of the sample according to the variation curve of the temperatureCWith MnO2The variation of the doping amount is shown in FIG. 9, from which it can be seen that TCWith MnO2Increase of doping amount monotonously decreases to below room temperature, and Ba with maximum electric strain0.70Ca0.30TiO3+0.6mol％MnO2T of ceramicsCThe temperature was 66 ℃.
As can be seen from fig. 3 to 9, Ba prepared in this embodiment mode0.70Ca0.30TiO3+0.6mol％MnO2The ceramic sample has the best comprehensive electricityThe performance parameters are as follows: relative dielectric constant εr1323, dielectric loss tangent tan δ 0.08, curie temperature TC66 ℃ maximum of polarization Pmax＝12.2μC/cm2Residual polarization Pr＝6.9μC/cm2Coercive field EC13.3kV/cm, piezoelectric constant d33116pC/N, planar electromechanical coupling coefficient kp0.22%, mechanical quality factor Qm684 inverse piezoelectric coefficient
Figure BDA0003555503350000081
Figure BDA0003555503350000082
Unilateral electrical strain Unipolar Smax0.75%, bilateral electrostrictive bipolar Smax0.56%, and the electric strain is even higher than that of commercial PZT ceramic and Bi reported in literature0.5Na0.5TiO3Based on lead-free ceramics, indicating Ba prepared in this embodiment0.70Ca0.30TiO3+x mol％MnO2(x ═ 0.55-0.65) lead-free piezoelectric ceramics exhibit large electrical strains at room temperature, making them of great potential for use in piezoelectric actuators.

Claims (5)

1. BaTiO with large room-temperature electrostrictive strain3The lead-free piezoelectric ceramic is characterized by its chemical formula Ba0.70Ca0.30TiO3+x mol％MnO2Wherein x is a mole fraction, and x is 0.6.
2. The room temperature large electrostrictive BaTiO of claim 1 in combination with a binder3The preparation method of the lead-free piezoelectric ceramic is characterized by comprising the following steps of:
firstly, mixing the raw material BaCO3、CaCO3、TiO2And MnO2According to the formula Ba0.70Ca0.30TiO3+x mol％MnO2Wherein x is 0.6;
mixing the raw materials weighed in the step one with absolute ethyl alcohol, putting the mixture into a planetary ball mill, performing wet ball milling for 22-24 hours at the rotating speed of 150-200 revolutions per minute, putting the slurry into a drying oven at 90 ℃, performing heat preservation for 3-4 hours, drying, and performing pressure preservation for 1-2 minutes at 10-16 MPa by using a tablet press to obtain a blank to be presintered, wherein the diameter of the blank is 55-60 mm, and the thickness of the blank is 4-6 mm; wherein the ratio of the mass of the absolute ethyl alcohol to the total mass of the raw materials is (1.2-1.6): 1; the grinding balls used for ball milling are composed of agate balls with the diameters of 20mm, 10mm and 6mm according to the number ratio of 1:10: 15;
thirdly, placing the blank to be presintered prepared in the second step into a muffle furnace, heating to 900-950 ℃ at the heating rate of 2-3 ℃/min, preserving heat for 2-4 h for presintering, and cooling along with the furnace to obtain a presintered tablet;
fourthly, crushing the pre-sintered tablets to 70-130 meshes of powder, mixing the powder with absolute ethyl alcohol, putting the powder into a ball milling tank, ball milling the powder for 22-24 hours at a rotating speed of 150-200 revolutions per minute by using a planetary ball mill, preserving heat for 3-4 hours at 90 ℃, drying slurry, adding 7 wt% of polyvinyl alcohol solution adhesive, averagely adding 1-1.5 drops of adhesive into every 1g of powder, placing the powder in the air for 22-24 hours, granulating, sieving the powder with 100 meshes and 150 meshes, taking 150 meshes of powder, keeping the powder at 5-7 MPa for 1-3 minutes by using a tablet machine to form a thin wafer blank with the diameter of 9-11 mm and the thickness of 0.5-1.0 mm, stacking the blanks up and down, covering and burying the blank with 100 meshes of powder, putting the blank into a muffle furnace, increasing the temperature to 600 ℃ at a heating rate of 2-4 ℃/min, preserving heat for 2 hours, removing the adhesive, cooling the blank along with the furnace, taking out the blank, putting the blank into the muffle furnace, sintering in a step-type heating mode, increasing the temperature to 800 ℃ at a heating rate of 2-4 ℃/min, heating to 1230-1340 ℃ at the heating rate of 1.5-2 ℃/min, preserving the temperature for 3-4 h in the air atmosphere, and naturally cooling to room temperature along with the furnace to obtain a ceramic blank, wherein the mass ratio of the mass of the absolute ethyl alcohol to the mass of the powder pre-sintered and pressed into sheets in the fourth step is (1.2-1.6): 1;
fifthly, embedding the ceramic blank into powder with the same components, heating to 800 ℃ at a heating rate of 1.5-3 ℃/min, keeping the temperature for 4-6 h in an air atmosphere for annealing, cooling to room temperature along with the furnace, adding deionized water into corundum powder, polishing a sample on a smooth glass plate, and obtaining BaTiO with large electrostrictive strain at room temperature3A lead-free piezoelectric ceramic.
3. The room temperature, large electrostrictive BaTiO of claim 2 in accordance with claim 23The preparation method of the lead-free piezoelectric ceramic is characterized in that x in the step one is 0.6.
4. BaTiO with large electrostriction at room temperature according to claim 2 or 33The preparation method of the lead-free piezoelectric ceramic is characterized in that the pre-sintering parameter in the third step is 900-950 ℃ heat preservation for 2-4 h and the sintering is carried out by heating in the fourth step in a staged manner, namely, the temperature is raised to 800 ℃ at the heating rate of 2-4 ℃/min and is preserved for 2h, and then the temperature is raised to 1230-1340 ℃ at the heating rate of 1.5-2 ℃/min and is preserved for 3-4 h in air for sintering.
5. BaTiO with large electrostriction at room temperature according to claim 43The preparation method of the lead-free piezoelectric ceramic is characterized in that in the fifth step, the annealing temperature of the ceramic blank is 800 ℃, and the annealing heat preservation time is 4-6 hours.
CN202210275000.7A 2022-03-21 2022-03-21 BaTiO with large room-temperature electrostrictive strain3Base leadless piezoelectric ceramic and preparation method thereof Pending CN114605146A (en)

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