CN116477938B - Barium titanate-based leadless piezoelectric ceramic and preparation method thereof - Google Patents

Barium titanate-based leadless piezoelectric ceramic and preparation method thereof Download PDF

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CN116477938B
CN116477938B CN202310438389.7A CN202310438389A CN116477938B CN 116477938 B CN116477938 B CN 116477938B CN 202310438389 A CN202310438389 A CN 202310438389A CN 116477938 B CN116477938 B CN 116477938B
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barium titanate
piezoelectric ceramic
heating
preserving heat
cooling
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CN116477938A (en
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刘峰
张曙光
高美珍
余腾飞
邱
柯超群
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Audiowell Electronics Guangdong Co ltd
Lanzhou University
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Audiowell Electronics Guangdong Co ltd
Lanzhou University
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Abstract

The invention relates to the technical field of piezoelectric ceramics, in particular to a preparation method of barium titanate-based leadless piezoelectric ceramics, which comprises the following steps: weighing raw materials, and pre-sintering to prepare a precursor; granulating and molding the precursor to prepare a ceramic blank; performing glue discharging, sintering, annealing, oxidation, silver burning and polarization on the ceramic blank to prepare the barium titanate-based leadless piezoelectric ceramic; wherein the raw materials comprise BaCO 3 and TiO 2; the general formula of the barium titanate-based leadless piezoelectric ceramic is BaTiO 3·xTiO2, and x is 0-0.005. The preparation method of the barium titanate-based leadless piezoelectric ceramic provided by the invention improves the piezoelectric performance of the barium titanate-based leadless piezoelectric ceramic by limiting the composition of the piezoelectric ceramic and introducing the oxidation step, and the piezoelectric coefficient of the barium titanate-based leadless piezoelectric ceramic can exceed 270pC/N at most and is far higher than that of the traditional barium titanate-based leadless piezoelectric ceramic.

Description

Barium titanate-based leadless piezoelectric ceramic and preparation method thereof
Technical Field
The invention relates to the technical field of piezoelectric ceramics, in particular to barium titanate-based lead-free piezoelectric ceramics and a preparation method thereof.
Background
The piezoelectric ceramic is a functional ceramic material capable of realizing the mutual conversion between electric energy and mechanical energy, and has wide application in the aspects of automobiles, household appliances, aerospace, navigation, military and the like. With the increasing development of electronic technology, piezoelectric ceramics play an increasingly important role in social development as a base stone of electronic equipment. In the past, lead-containing piezoelectric ceramics occupy the main position in the field of piezoelectric ceramics, but the lead content of the lead-containing piezoelectric ceramics reaches more than 80 percent, and the lead-containing piezoelectric ceramics can cause serious threat to the environment in the production, use and scrapping stages, so the development of lead-free piezoelectric ceramics is urgent.
The barium titanate-based lead-free piezoelectric ceramic applied to the past more than eighty years is the lead-free piezoelectric ceramic applied to the earliest large scale. The barium titanate-based lead-free piezoelectric ceramic prepared by the traditional preparation method has the defects of microcracks, hollows, oxygen vacancies and the like, so that the piezoelectric coefficient (d 33) of the piezoelectric ceramic is usually only about 170pC/N, and the maximum piezoelectric coefficient is only 190pC/N, which greatly limits the application of the barium titanate-based lead-free piezoelectric ceramic.
Therefore, how to obtain a barium titanate-based lead-free piezoelectric ceramic with a relatively high piezoelectric coefficient has been a problem to be solved.
Disclosure of Invention
Based on this, it is necessary to provide a barium titanate-based lead-free piezoelectric ceramic having a relatively high piezoelectric coefficient and a method for producing the same.
One aspect of the present invention provides a method for preparing barium titanate-based leadless piezoelectric ceramics, comprising the steps of:
Weighing raw materials, and pre-sintering to prepare a precursor;
granulating and molding the precursor to prepare a ceramic blank;
Performing glue discharging, sintering, annealing, oxidation, silver burning and polarization on the ceramic blank to prepare the barium titanate-based leadless piezoelectric ceramic;
Wherein the raw materials comprise BaCO 3 and TiO 2; the general formula of the barium titanate-based leadless piezoelectric ceramic is BaTiO 3·xTiO2, and x is 0-0.005.
In one embodiment, the oxidizing comprises the steps of: heating the ceramic body to 1250-1300 ℃, preserving heat for 2-4 h, and cooling to room temperature.
In one embodiment, the cooling rate is 2 ℃/min to 5 ℃/min.
In one embodiment, the step of pre-sintering is preceded by the steps of mixing, first pulverizing, and first drying the raw materials.
In one embodiment, the step of granulating is preceded by the steps of second pulverizing the precursor and second drying.
In one embodiment, before the annealing step, the method further includes a step of polishing the sintered material, wherein the polishing conditions include: polishing with 1200-8000 mesh sand paper.
In one embodiment, the method for preparing the barium titanate-based leadless piezoelectric ceramics satisfies one of the following conditions:
the presintering comprises the following steps: heating the raw materials to 1000-1200 ℃, and preserving heat for 2-4 hours;
The glue discharging comprises the following steps: heating the ceramic blank to 600-650 ℃, and preserving heat for 3-4 hours;
the sintering comprises the following steps: heating the material after glue discharge to 1300-1400 ℃, and preserving heat for 3-4 hours;
the annealing includes the steps of: heating the sintered material to 1000-1100 ℃, and preserving heat for 2.5-3 hours;
the silver burning comprises the following steps: heating the oxidized material to 800-850 ℃, and preserving heat for 30-50 min.
In one embodiment, the polarization condition includes: the polarization electric field is 4.2 kV/mm-4.5 kV/mm, the polarization temperature is 28-32 ℃, and the polarization time is 25-40 min.
In still another aspect, the present invention provides a barium titanate-based leadless piezoelectric ceramic, which is prepared by the method for preparing the barium titanate-based leadless piezoelectric ceramic.
In yet another aspect of the present invention, an electronic component is provided that includes the barium titanate-based leadless piezoelectric ceramic described above.
The preparation method of the barium titanate-based leadless piezoelectric ceramic provided by the invention improves the piezoelectric performance of the barium titanate-based leadless piezoelectric ceramic by limiting the composition of the piezoelectric ceramic and introducing the oxidation step, and the piezoelectric coefficient of the barium titanate-based leadless piezoelectric ceramic exceeds 270pC/N and is far higher than the piezoelectric coefficient (-190 pC/N) of the traditional barium titanate-based leadless piezoelectric ceramic.
In addition, the average grain size of the barium titanate-based leadless piezoelectric ceramic provided by the invention can reach 25-45 mu m, and the barium titanate-based leadless piezoelectric ceramic is a micron-sized material. Compared with the traditional nano-scale barium titanate-based leadless piezoelectric ceramics, the piezoelectric ceramics have better practical effect and economic benefit.
The barium titanate-based leadless piezoelectric ceramic provided by the invention has great performance breakthrough and practicality, and can be used for preparing electronic elements in electronic devices such as piezoelectric buzzers, high-frequency filters and the like.
Drawings
FIG. 1 is an XRD pattern of barium titanate-based lead-free piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2;
FIG. 2 is a scanning electron microscope image of the barium titanate-based leadless piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2;
FIG. 3 shows average crystal grain sizes of barium titanate-based lead-free piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2;
FIG. 4 is a graph showing the relative densities of barium titanate-based leadless piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2;
FIG. 5 shows the hysteresis loops of the barium titanate-based leadless piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2;
FIG. 6 is a saturated remnant polarization P max, remnant polarization Pr, and coercive field E c of the barium titanate-based leadless piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2;
FIG. 7 shows the relative dielectric constants ε r of the barium titanate-based leadless piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2;
Fig. 8 shows the product of the piezoelectric coefficients d 33 and epsilon rPr of the barium titanate-based leadless piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
One aspect of the present invention provides a method for preparing barium titanate-based leadless piezoelectric ceramics, comprising the steps of:
s110, weighing raw materials, and pre-sintering to prepare a precursor. Wherein the raw materials comprise BaCO 3 and TiO 2; the general formula of the barium titanate-based leadless piezoelectric ceramic is BaTiO 3·xTiO2, and x is 0-0.01.
In one example, x may be 0.001, 0.002, 0.003, 0.004, or 0.005.
In one example, the raw materials are weighed according to the composition formula of the barium titanate-based lead-free piezoelectric ceramic.
In one example, the method further comprises the steps of mixing, first crushing and first drying the raw materials before the step of sintering.
Alternatively, the first pulverizing method is ball milling. Wherein, the particle size of ball-milled ball-milling beads is 2 mm-10 mm, the rotating speed is 410 r/min-460 r/min, and the time is 16 h-18 h.
Optionally, the solvent for ball milling is absolute ethanol.
Optionally, during ball milling, the raw materials: ball milling: the volume ratio of the absolute ethyl alcohol is 1-2 to 8-10 to 5-6.
Optionally, the temperature of the first drying is 120-150 ℃.
Optionally, the dried material is sieved by a 60-100-mesh sieve.
In one example, the pre-sintering includes the steps of: heating the raw materials to 1000-1200 ℃, and preserving heat for 2-4 h.
In one example, the heating rate is 10 ℃/min to 20 ℃/min.
S120, granulating and molding the precursor to prepare a ceramic blank.
In one example, the method further includes the steps of pulverizing the precursor a second time and drying the precursor a second time before the granulating step.
Alternatively, the second comminution process is ball milling. Wherein, the particle size of ball-milled ball-milling beads is 2 mm-10 mm, the rotating speed is 410 r/min-460 r/min, and the time is 18 h-24 h.
Optionally, the solvent for ball milling is absolute ethanol.
Optionally, during ball milling, the precursor: ball milling: the volume ratio of the absolute ethyl alcohol is 1-2 to 8-10 to 5-6.
Optionally, the temperature of the second drying is 120-150 ℃.
Optionally, after the second drying, the particle size of the precursor is 180-240 meshes.
In one example, the precursor is added to an aqueous solution of polyvinyl alcohol having a concentration of 3wt% to 5wt% for granulation.
In one example, the granulated material is molded for 4 to 8 minutes under the pressure of 4 to 10 MPa. The mold used for molding is, without limitation, 12#.
S130, performing glue discharging, sintering, annealing, oxidation, silver burning and polarization on the ceramic blank to prepare the barium titanate-based leadless piezoelectric ceramic.
In one example, the adhesive discharging includes the following steps: heating the ceramic body to 600-650 ℃, preserving heat for 3-4 h, and cooling to room temperature. Wherein the heating rate of heating is 3 ℃/min to 5 ℃/min.
Further, in the process of discharging the glue, the ceramic body is contacted with air.
In one example, the sintering includes the steps of: heating the material after glue discharge to 1300-1400 ℃, preserving heat for 3-4 h, and cooling to room temperature. Wherein the heating rate of heating is 3 ℃/min to 5 ℃/min.
In one example, the step of annealing is preceded by a step of polishing the sintered material. Specifically, the above polishing conditions include: and polishing by adopting sand paper with the model of 1200-8000 meshes.
In one example, the annealing includes the steps of: heating the ceramic blank to 1000-1100 deg.c and maintaining for 2.5-3 hr. Wherein the heating rate of heating is 3 ℃/min to 5 ℃/min.
In one example, the annealing further includes a step of cooling the incubated material to a temperature below 100 ℃, wherein the cooling rate is between 5 ℃/min and 10 ℃/min.
In one example, the oxidation includes the steps of: heating the ceramic body to 1250-1300 ℃, preserving heat for 2-4 h, and cooling to room temperature.
In one example, the heating rate is 5 to 10 ℃.
In one example, the cooling rate is 2 ℃/min to 5 ℃/min.
In one example, the silver firing includes the following steps: heating the oxidized material to 800-850 ℃, and preserving heat for 30-50 min.
In one example, the step of firing silver further includes, before heating, coating a thin silver paste with a thickness of 0.03mm to 0.05mm on the surface of the oxidized material.
In one example, the silver burned material is polarized in silicone oil.
In one example, the polarization conditions include: the polarization electric field is 4.2 kV/mm-4.5 kV/mm, the polarization temperature is 28-32 ℃, and the polarization time is 25-40 min.
In one example, the step of polarizing is preceded by the step of polishing the silver burned material. Optionally, sand paper with 8000-10000 meshes is adopted to polish the silver-burned material.
In one example, the preparation method of the barium titanate-based leadless piezoelectric ceramic comprises the following steps:
S1, weighing raw materials BaCO 3 and TiO 2 according to a composition general formula BaTiO 3·xTiO2 of the barium titanate-based leadless piezoelectric ceramic, wherein x is 0-0.01.
S2, mixing the raw materials, crushing for the first time and drying for the first time. Wherein the first grinding method is ball milling, the particle size of ball milling beads is 2 mm-10 mm, the rotating speed is 410 r/min-460 r/min, the time is 16 h-18 h, the ball milling solvent is absolute ethyl alcohol, and the volume ratio of raw materials, ball milling beads and absolute ethyl alcohol is (1-2) to (8-10) to (5-6) in the ball milling process. The temperature of the first drying is 120-150 ℃. After the first drying, the dried material is sieved by a 60-100 mesh sieve.
S3, heating the sieved material to 1000-1200 ℃ at a heating rate of 10-20 ℃/min, preserving heat for 2-4 h, pre-sintering, and cooling to 25-200 ℃ to prepare the precursor.
S4, carrying out secondary crushing and secondary drying on the precursor. Wherein the second grinding method is ball milling, the particle size of ball milling beads is 2 mm-10 mm, the rotating speed is 410 r/min-460 r/min, the time is 18 h-24 h, the ball milling solvent is absolute ethyl alcohol, and the volume ratio of precursor, ball milling beads and absolute ethyl alcohol is (1-2) to (8-10) to (5-6) in the ball milling process. The temperature of the second drying is 120-150 ℃. And after the second drying, sieving the dried material with a 180-240 mesh sieve.
S5, adding the sieved precursor into a polyvinyl alcohol aqueous solution with the concentration of 3-5 wt% for granulating, and molding the granulated material under the pressure of 4-10 MPa for 4-8 min to prepare a ceramic blank.
S6, heating the ceramic blank to 600-650 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 3-4 h, cooling to room temperature, and discharging glue. In the process of discharging glue, the ceramic blank body is contacted with air.
S7, heating the material subjected to glue discharging to 1300-1400 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 3-4 hours, sintering, and cooling to room temperature.
S8, polishing the sintered material by adopting sand paper with the model of 1200-8000 meshes until the surface is smooth and flat, and a blurred figure appears.
S9, heating the polished ceramic blank to 1000-1100 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 2.5-3 h, and cooling to below 100 ℃ at a cooling rate of 5-10 ℃/min for annealing.
S10, heating the annealed ceramic blank to 1250-1300 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 2-4 h, and cooling to room temperature at a cooling rate of 2-5 ℃/min for oxidation.
S11, coating thin silver paste with the thickness of 0.03-0.05 mm on the surface of the oxidized material, heating to 800-850 ℃, preserving heat for 30-50min, burning silver, and cooling to room temperature.
S12, polishing the silver electrode of the silver-burned material by using 8000-10000-mesh sand paper until the surface is smooth, and displaying a clear figure.
S13, placing the polished material into silicone oil, and polarizing for 25-40 min under the condition that the polarizing electric field is 4.2 kV/mm-4.5 kV/mm and the polarizing temperature is 28-32 ℃ to prepare the barium titanate-based leadless piezoelectric ceramic.
The preparation method of the piezoelectric ceramic provided by the invention improves the piezoelectric coefficient of the piezoelectric ceramic by limiting the composition of the piezoelectric ceramic and introducing the oxidation step.
In still another aspect, the present invention provides a barium titanate-based leadless piezoelectric ceramic, which is prepared by the method for preparing the barium titanate-based leadless piezoelectric ceramic.
In yet another aspect of the present invention, an electronic component is provided that includes the barium titanate-based leadless piezoelectric ceramic described above.
The following are specific examples:
Example 1
The preparation method of the barium titanate-based leadless piezoelectric ceramics provided by the embodiment comprises the following steps:
(1) Raw materials BaCO 3 and TiO 2 are weighed according to a composition general formula BaTiO 3·0.005TiO2 of the barium titanate-based leadless piezoelectric ceramic.
(2) Mixing the raw materials, ball milling for 16 hours at the rotating speed of 410r/min by adopting agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively, wherein the volume ratio of the raw materials to the ball milling beads to the absolute ethyl alcohol is 1:8:5 in the ball milling process. Drying at 120deg.C, and sieving with 80 mesh sieve.
(3) And (3) placing the sieved material into a covered crucible, placing the crucible into a muffle furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and pre-sintering to obtain the precursor. Cooling to 200 ℃, taking out, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(4) The precursor is ball-milled for 20 hours by agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively at the rotating speed of 460r/min, and the volume ratio of raw materials, ball-milled beads and absolute ethyl alcohol is 1:8:5 in the ball-milling process. Drying at 120deg.C, and sieving with 180 mesh sieve.
(5) Adding the sieved precursor into a polyvinyl alcohol (PVA) aqueous solution with the concentration of 3wt percent for granulating, putting the granulated material into a steel mould with the model number of 12# and molding for 4min under the pressure of 4MPa to prepare a ceramic blank.
(6) And (3) placing the ceramic blank in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, discharging glue, and cooling to room temperature. In the heating, heat preservation and cooling processes, the muffle furnace keeps the furnace door open in the whole process, so that the ceramic green body contacts with air, and the furnace door is closed after cooling is finished.
(7) And (3) heating the material in the step (6) to 1300 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, sintering, cooling to room temperature, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(8) And (3) polishing the material in the step (7) by adopting sand paper with 1200 meshes, 5000 meshes and 8000 meshes in sequence until the surface is smooth and flat, and a blurred figure appears.
(9) Heating the material in the step (8) to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, cooling to below 100 ℃ at a cooling rate of 10 ℃/min, and annealing.
(10) And (3) heating the material in the step (9) to 1250 ℃ at a heating rate of 10 ℃/min in air, preserving heat for 2 hours, and cooling to room temperature at a cooling rate of 2 ℃/min for oxidation.
(11) Coating the surface of the material obtained in the step (10) with thin silver paste with the thickness of 0.05mm, heating to 850 ℃, preserving heat for 30min, sintering silver, and cooling to room temperature.
(12) And (3) sequentially polishing the silver electrode of the silver-burned material with 8000-mesh and 10000-mesh sand paper until the surface is smooth, and displaying a clear figure.
(13) And (3) putting the polished material into silicone oil, and polarizing for 25 minutes under the condition that the polarizing electric field is 4.2kV/mm and the polarizing temperature is 30 ℃ to obtain the barium titanate-based lead-free piezoelectric ceramic.
Example 2
The preparation method of the barium titanate-based leadless piezoelectric ceramics provided by the embodiment comprises the following steps:
(1) Raw materials BaCO 3 and TiO 2 are weighed according to a composition general formula BaTiO 3·0.005TiO2 of the barium titanate-based leadless piezoelectric ceramic.
(2) Mixing the raw materials, ball milling for 16 hours at the rotating speed of 410r/min by adopting agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively, wherein the volume ratio of the raw materials to the ball milling beads to the absolute ethyl alcohol is 1:8:5 in the ball milling process. Drying at 120deg.C, and sieving with 80 mesh sieve.
(3) And (3) placing the sieved material into a covered crucible, placing the crucible into a muffle furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and pre-sintering to obtain the precursor. Cooling to 200 ℃, taking out, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(4) The precursor is ball-milled for 20 hours by agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively at the rotating speed of 460r/min, and the volume ratio of raw materials, ball-milled beads and absolute ethyl alcohol is 1:8:5 in the ball-milling process. Drying at 120deg.C, and sieving with 180 mesh sieve.
(5) Adding the sieved precursor into a polyvinyl alcohol (PVA) aqueous solution with the concentration of 3wt percent for granulating, putting the granulated material into a steel mould with the model number of 12# and molding for 4min under the pressure of 4MPa to prepare a ceramic blank.
(6) And (3) placing the ceramic blank in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, discharging glue, and cooling to room temperature. In the heating, heat preservation and cooling processes, the muffle furnace keeps the furnace door open in the whole process, so that the ceramic green body contacts with air, and the furnace door is closed after cooling is finished.
(7) Heating the material in the step (6) to 1325 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, sintering, cooling to room temperature, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(8) And (3) polishing the material in the step (7) by adopting sand paper with 1200 meshes, 5000 meshes and 8000 meshes in sequence until the surface is smooth and flat, and a blurred figure appears.
(9) Heating the material in the step (8) to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, cooling to below 100 ℃ at a cooling rate of 10 ℃/min, and annealing.
(10) And (3) heating the material in the step (9) to 1250 ℃ at a heating rate of 10 ℃/min in air, preserving heat for 2 hours, and cooling to room temperature at a cooling rate of 2 ℃/min for oxidation.
(11) Coating the surface of the material obtained in the step (10) with thin silver paste with the thickness of 0.05mm, heating to 850 ℃, preserving heat for 30min, sintering silver, and cooling to room temperature.
(12) And (3) sequentially polishing the silver electrode of the silver-burned material with 8000-mesh and 10000-mesh sand paper until the surface is smooth, and displaying a clear figure.
(13) And (3) putting the polished material into silicone oil, and polarizing for 25 minutes under the condition that the polarizing electric field is 4.2kV/mm and the polarizing temperature is 30 ℃ to obtain the barium titanate-based lead-free piezoelectric ceramic.
Example 3
The preparation method of the barium titanate-based leadless piezoelectric ceramics provided by the embodiment comprises the following steps:
(1) Raw materials BaCO 3 and TiO 2 are weighed according to a composition general formula BaTiO 3·0.005TiO2 of the barium titanate-based leadless piezoelectric ceramic.
(2) Mixing the raw materials, ball milling for 16 hours at the rotating speed of 410r/min by adopting agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3, and during the ball milling process, the raw materials are: ball milling: the volume ratio of the absolute ethyl alcohol is 1:8:5. Drying at 120deg.C, and sieving with 80 mesh sieve.
(3) And (3) placing the sieved material into a covered crucible, placing the crucible into a muffle furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and pre-sintering to obtain the precursor. Cooling to 200 ℃, taking out, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(4) The precursor is ball-milled for 20 hours by agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively at the rotating speed of 460r/min, and the volume ratio of raw materials, ball-milled beads and absolute ethyl alcohol is 1:8:5 in the ball-milling process. Drying at 120deg.C, and sieving with 180 mesh sieve.
(5) Adding the sieved precursor into a polyvinyl alcohol (PVA) aqueous solution with the concentration of 3wt percent for granulating, putting the granulated material into a steel mould with the model number of 12# and molding for 4min under the pressure of 4MPa to prepare a ceramic blank.
(6) And (3) placing the ceramic blank in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, discharging glue, and cooling to room temperature. In the heating, heat preservation and cooling processes, the muffle furnace keeps the furnace door open in the whole process, so that the ceramic green body contacts with air, and the furnace door is closed after cooling is finished.
(7) Heating the material in the step (6) to 1350 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, sintering, cooling to room temperature, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(8) And (3) polishing the material in the step (7) by adopting sand paper with 1200 meshes, 5000 meshes and 8000 meshes in sequence until the surface is smooth and flat, and a blurred figure appears.
(9) Heating the material in the step (8) to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, cooling to below 100 ℃ at a cooling rate of 10 ℃/min, and annealing.
(10) And (3) heating the material in the step (9) to 1250 ℃ at a heating rate of 10 ℃/min in air, preserving heat for 2 hours, and cooling to room temperature at a cooling rate of 2 ℃/min for oxidation.
(11) Coating the surface of the material obtained in the step (10) with thin silver paste with the thickness of 0.05mm, heating to 850 ℃, preserving heat for 30min, sintering silver, and cooling to room temperature.
(12) And (3) sequentially polishing the silver electrode of the silver-burned material with 8000-mesh and 10000-mesh sand paper until the surface is smooth, and displaying a clear figure.
(13) And (3) putting the polished material into silicone oil, and polarizing for 25 minutes under the condition that the polarizing electric field is 4.2kV/mm and the polarizing temperature is 30 ℃ to obtain the barium titanate-based lead-free piezoelectric ceramic.
Example 4
The preparation method of the barium titanate-based leadless piezoelectric ceramics provided by the embodiment comprises the following steps:
(1) Raw materials BaCO 3 and TiO 2 are weighed according to a composition general formula BaTiO 3·0.005TiO2 of the barium titanate-based leadless piezoelectric ceramic.
(2) Mixing the raw materials, ball milling for 16 hours at the rotating speed of 410r/min by adopting agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively, wherein the volume ratio of the raw materials to the ball milling beads to the absolute ethyl alcohol is 1:8:5 in the ball milling process. Drying at 120deg.C, and sieving with 80 mesh sieve.
(3) And (3) placing the sieved material into a covered crucible, placing the crucible into a muffle furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and pre-sintering to obtain the precursor. Cooling to 200 ℃, taking out, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(4) The precursor is ball-milled for 20 hours by agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively at the rotating speed of 460r/min, and the volume ratio of raw materials, ball-milled beads and absolute ethyl alcohol is 1:8:5 in the ball-milling process. Drying at 120deg.C, and sieving with 180 mesh sieve.
(5) Adding the sieved precursor into a polyvinyl alcohol (PVA) aqueous solution with the concentration of 3wt percent for granulating, putting the granulated material into a steel mould with the model number of 12# and molding for 4min under the pressure of 4MPa to prepare a ceramic blank.
(6) And (3) placing the ceramic blank in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, discharging glue, and cooling to room temperature. In the heating, heat preservation and cooling processes, the muffle furnace keeps the furnace door open in the whole process, so that the ceramic green body contacts with air, and the furnace door is closed after cooling is finished.
(7) Heating the material in the step (6) to 1375 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, sintering, cooling to room temperature, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(8) And (3) polishing the material in the step (7) by adopting sand paper with the model of 1200 meshes, 5000 meshes and 8000 meshes in sequence until the surface is smooth and even, and a blurred figure appears.
(9) Heating the material in the step (8) to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, cooling to below 100 ℃ at a cooling rate of 10 ℃/min, and annealing.
(10) And (3) heating the material in the step (9) to 1250 ℃ at a heating rate of 10 ℃/min in air, preserving heat for 2 hours, and cooling to room temperature at a cooling rate of 2 ℃/min for oxidation.
(11) Coating the surface of the material obtained in the step (10) with thin silver paste with the thickness of 0.05mm, heating to 850 ℃, preserving heat for 30min, sintering silver, and cooling to room temperature.
(12) And (3) sequentially polishing the silver electrode of the silver-burned material with 8000-mesh and 10000-mesh sand paper until the surface is smooth, and displaying a clear figure.
(13) And (3) putting the polished material into silicone oil, and polarizing for 25 minutes under the condition that the polarizing electric field is 4.2kV/mm and the polarizing temperature is 30 ℃ to obtain the barium titanate-based lead-free piezoelectric ceramic.
Example 5
The preparation method of the barium titanate-based leadless piezoelectric ceramics provided by the embodiment comprises the following steps:
(1) Raw materials BaCO 3 and TiO 2 are weighed according to a composition general formula BaTiO 3·0.005TiO2 of the barium titanate-based leadless piezoelectric ceramic.
(2) Mixing the raw materials, ball milling for 16 hours at the rotating speed of 410r/min by adopting agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3, and during the ball milling process, the raw materials are: ball milling: the volume ratio of the absolute ethyl alcohol is 1:8:5. Drying at 120deg.C, and sieving with 80 mesh sieve.
(3) And (3) placing the sieved material into a covered crucible, placing the crucible into a muffle furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and pre-sintering to obtain the precursor. Cooling to 200 ℃, taking out, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(4) The precursor is ball-milled for 20 hours by agate beads with the particle size of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 at the rotating speed of 460r/min, and the volume ratio of raw materials, ball-milled beads and absolute ethyl alcohol is 1:8:5 in the ball-milling process. Drying at 120deg.C, and sieving with 180 mesh sieve.
(5) Adding the sieved precursor into a polyvinyl alcohol (PVA) aqueous solution with the concentration of 3wt percent for granulating, putting the granulated material into a steel mould with the model number of 12# and molding for 4min under the pressure of 4MPa to prepare a ceramic blank.
(6) And (3) placing the ceramic blank in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, discharging glue, and cooling to room temperature. In the heating, heat preservation and cooling processes, the muffle furnace keeps the furnace door open in the whole process, so that the ceramic green body contacts with air, and the furnace door is closed after cooling is finished.
(7) Heating the material in the step (6) to 1400 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, sintering, cooling to room temperature, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(8) And (3) polishing the material in the step (7) by adopting sand paper with the model of 1200 meshes, 5000 meshes and 8000 meshes in sequence until the surface is smooth and even, and a blurred figure appears.
(9) Heating the material in the step (8) to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, cooling to below 100 ℃ at a cooling rate of 10 ℃/min, and annealing.
(10) And (3) heating the material in the step (9) to 1250 ℃ at a heating rate of 10 ℃/min in air, preserving heat for 2 hours, and cooling to room temperature at a cooling rate of 2 ℃/min for oxidation.
(11) Coating the surface of the material obtained in the step (10) with thin silver paste with the thickness of 0.05mm, heating to 850 ℃, preserving heat for 30min, sintering silver, and cooling to room temperature.
(12) And (3) sequentially polishing the silver electrode of the silver-burned material with 8000-mesh and 10000-mesh sand paper until the surface is smooth, and displaying a clear figure.
(13) And (3) putting the polished material into silicone oil, and polarizing for 25 minutes under the condition that the polarizing electric field is 4.2kV/mm and the polarizing temperature is 30 ℃ to obtain the barium titanate-based lead-free piezoelectric ceramic.
Example 6
The preparation method of the barium titanate-based leadless piezoelectric ceramics provided by the embodiment comprises the following steps:
(1) According to the composition general formula BaTiO 3 (namely x is 0) of the barium titanate-based leadless piezoelectric ceramic, raw materials BaCO 3 and TiO 2 are weighed.
(2) Mixing the raw materials, ball milling for 16 hours at the rotating speed of 410r/min by adopting agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively, wherein the volume ratio of the raw materials to the ball milling beads to the absolute ethyl alcohol is 1:8:5 in the ball milling process. Drying at 120deg.C, and sieving with 80 mesh sieve.
(3) And (3) placing the sieved material into a covered crucible, placing the crucible into a muffle furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and pre-sintering to obtain the precursor. Cooling to 200 ℃, taking out, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(4) The precursor is ball-milled for 20 hours by agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively at the rotating speed of 460r/min, and the volume ratio of raw materials, ball-milled beads and absolute ethyl alcohol is 1:8:5 in the ball-milling process. Drying at 120deg.C, and sieving with 180 mesh sieve.
(5) Adding the sieved precursor into a polyvinyl alcohol (PVA) aqueous solution with the concentration of 3wt percent for granulating, putting the granulated material into a steel mould with the model number of 12# and molding for 4min under the pressure of 4MPa to prepare a ceramic blank.
(6) And (3) placing the ceramic blank in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, discharging glue, and cooling to room temperature. In the heating, heat preservation and cooling processes, the muffle furnace keeps the furnace door open in the whole process, so that the ceramic green body contacts with air, and the furnace door is closed after cooling is finished.
(7) Heating the material in the step (6) to 1350 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, sintering, cooling to room temperature, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(8) And (3) polishing the material in the step (7) by adopting sand paper with the model of 1200 meshes, 5000 meshes and 8000 meshes in sequence until the surface is smooth and even, and a blurred figure appears.
(9) Heating the material in the step (8) to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, cooling to below 100 ℃ at a cooling rate of 10 ℃/min, and annealing.
(10) And (3) heating the material in the step (9) to 1250 ℃ at a heating rate of 10 ℃/min in air, preserving heat for 2 hours, and cooling to room temperature at a cooling rate of 2 ℃/min for oxidation.
(11) Coating the surface of the material obtained in the step (10) with thin silver paste with the thickness of 0.05mm, heating to 850 ℃, preserving heat for 30min, sintering silver, and cooling to room temperature.
(12) And (3) sequentially polishing the silver electrode of the silver-burned material with 8000-mesh and 10000-mesh sand paper until the surface is smooth, and displaying a clear figure.
(13) And (3) putting the polished material into silicone oil, and polarizing for 25 minutes under the condition that the polarizing electric field is 4.2kV/mm and the polarizing temperature is 30 ℃ to obtain the barium titanate-based lead-free piezoelectric ceramic.
Example 7
The preparation method of the barium titanate-based leadless piezoelectric ceramics provided by the embodiment comprises the following steps:
(1) Raw materials BaCO 3 and TiO 2 are weighed according to a composition general formula BaTiO 3·0.001TiO2 of the barium titanate-based leadless piezoelectric ceramic.
(2) Mixing the raw materials, ball milling for 16 hours at the rotating speed of 410r/min by adopting agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively, wherein the volume ratio of the raw materials to the ball milling beads to the absolute ethyl alcohol is 1:8:5 in the ball milling process. Drying at 120deg.C, and sieving with 80 mesh sieve.
(3) And (3) placing the sieved material into a covered crucible, placing the crucible into a muffle furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and pre-sintering to obtain the precursor. Cooling to 200 ℃, taking out, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(4) The precursor is ball-milled for 20 hours by agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively at the rotating speed of 460r/min, and the volume ratio of raw materials, ball-milled beads and absolute ethyl alcohol is 1:8:5 in the ball-milling process. Drying at 120deg.C, and sieving with 180 mesh sieve.
(5) Adding the sieved precursor into a polyvinyl alcohol (PVA) aqueous solution with the concentration of 3wt percent for granulating, putting the granulated material into a steel mould with the model number of 12# and molding for 4min under the pressure of 4MPa to prepare a ceramic blank.
(6) And (3) placing the ceramic blank in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, discharging glue, and cooling to room temperature. In the heating, heat preservation and cooling processes, the muffle furnace keeps the furnace door open in the whole process, so that the ceramic green body contacts with air, and the furnace door is closed after cooling is finished.
(7) Heating the material in the step (6) to 1350 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, sintering, cooling to room temperature, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(8) And (3) polishing the material in the step (7) by adopting sand paper with the model of 1200 meshes, 5000 meshes and 8000 meshes in sequence until the surface is smooth and even, and a blurred figure appears.
(9) Heating the material in the step (8) to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, cooling to below 100 ℃ at a cooling rate of 10 ℃/min, and annealing.
(10) And (3) heating the material in the step (9) to 1250 ℃ at a heating rate of 10 ℃/min in air, preserving heat for 2 hours, and cooling to room temperature at a cooling rate of 2 ℃/min for oxidation.
(11) Coating the surface of the material obtained in the step (10) with thin silver paste with the thickness of 0.05mm, heating to 850 ℃, preserving heat for 30min, sintering silver, and cooling to room temperature.
(12) And (3) sequentially polishing the silver electrode of the silver-burned material with 8000-mesh and 10000-mesh sand paper until the surface is smooth, and displaying a clear figure.
(13) And (3) putting the polished material into silicone oil, and polarizing for 25 minutes under the condition that the polarizing electric field is 4.2kV/mm and the polarizing temperature is 30 ℃ to obtain the barium titanate-based lead-free piezoelectric ceramic.
Comparative example 1
The preparation method of the barium titanate-based leadless piezoelectric ceramics provided by the comparative example comprises the following steps:
(1) Raw materials BaCO 3 and TiO 2 are weighed according to a composition general formula BaTiO 3·0.005TiO2 of the barium titanate-based leadless piezoelectric ceramic.
(2) Mixing the raw materials, ball milling for 18 hours at a rotating speed of 410r/min by adopting agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in a ratio of 1:1:3, wherein the volume ratio of the raw materials to the ball milling beads to the absolute ethyl alcohol is 1:8:5 in the ball milling process. Drying at 120deg.C, and sieving with 80 mesh sieve.
(3) And (3) placing the sieved material into a covered crucible, placing the crucible into a muffle furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and pre-sintering to obtain the precursor. Cooling to 200 ℃, taking out, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(4) The precursor is ball-milled for 20 hours by agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively at the rotating speed of 460r/min, and the volume ratio of raw materials, ball-milled beads and absolute ethyl alcohol is 1:8:5 in the ball-milling process. Drying at 120deg.C, and sieving with 180 mesh sieve.
(5) Adding the sieved precursor into a polyvinyl alcohol (PVA) aqueous solution with the concentration of 3wt percent for granulating, putting the granulated material into a steel mould with the model number of 12# and molding for 4min under the pressure of 4MPa to prepare a ceramic blank.
(6) And (3) placing the ceramic blank in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, discharging glue, and cooling to room temperature. In the heating, heat preservation and cooling processes, the muffle furnace keeps the furnace door open in the whole process, so that the ceramic green body contacts with air, and the furnace door is closed after cooling is finished.
(7) And (3) heating the material in the step (6) to 1300 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, sintering, cooling to room temperature, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(8) And (3) polishing the material in the step (7) by adopting sand paper with 1200 meshes, 5000 meshes and 8000 meshes in sequence until the surface is smooth and flat, and a blurred figure appears.
(9) Heating the material in the step (8) to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, cooling to below 100 ℃ at a cooling rate of 10 ℃/min, and annealing.
(10) Coating the surface of the material obtained in the step (9) with thin silver paste with the thickness of 0.05mm, heating to 850 ℃, preserving heat for 30min, sintering silver, and cooling to room temperature.
(11) And (3) sequentially polishing the silver electrode of the silver-burned material with 8000-mesh and 10000-mesh sand paper until the surface is smooth, and displaying a clear figure.
(12) And (3) putting the polished material into silicone oil, and polarizing for 25 minutes under the condition that the polarizing electric field is 4.2kV/mm and the polarizing temperature is 30 ℃ to obtain the barium titanate-based lead-free piezoelectric ceramic.
Comparative example 2
The preparation method of the barium titanate-based leadless piezoelectric ceramics provided by the comparative example comprises the following steps:
(1) Raw materials BaCO 3 and TiO 2 are weighed according to a composition general formula BaTiO 3·0.01TiO2 of the barium titanate-based leadless piezoelectric ceramic.
(2) Mixing the raw materials, ball milling for 16 hours at the rotating speed of 410r/min by adopting agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively, wherein the volume ratio of the raw materials to the ball milling beads to the absolute ethyl alcohol is 1:8:5 in the ball milling process. And then drying at 120 ℃ and sieving with a 80-mesh sieve.
(3) And (3) placing the sieved material into a covered crucible, placing the crucible into a muffle furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and pre-sintering to obtain the precursor. Cooling to 200 ℃, taking out, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(4) The precursor is ball-milled for 20 hours by agate beads with the particle sizes of 10mm, 5mm and 2mm mixed in the proportion of 1:1:3 respectively at the rotating speed of 460r/min, and the volume ratio of raw materials, ball-milled beads and absolute ethyl alcohol is 1:8:5 in the ball-milling process. Drying at 120deg.C, and sieving with 180 mesh sieve.
(5) Adding the sieved precursor into a polyvinyl alcohol (PVA) aqueous solution with the concentration of 3wt percent for granulating, putting the granulated material into a steel mould with the model number of 12# and molding for 4min under the pressure of 4MPa to prepare a ceramic blank.
(6) And (3) placing the ceramic blank in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, discharging glue, and cooling to room temperature. In the heating, heat preservation and cooling processes, the muffle furnace keeps the furnace door open in the whole process, so that the ceramic green body contacts with air, and the furnace door is closed after cooling is finished.
(7) Heating the material in the step (6) to 1350 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, sintering, cooling to room temperature, and regulating the actual temperature in the muffle furnace by using a FERRO temperature measuring ring.
(8) And (3) polishing the material in the step (7) by adopting sand paper with the model of 1200 meshes, 5000 meshes and 8000 meshes in sequence until the surface is smooth and even, and a blurred figure appears.
(9) Heating the material in the step (8) to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, cooling to below 100 ℃ at a cooling rate of 10 ℃/min, and annealing.
(10) And (3) heating the material in the step (9) to 1250 ℃ at a heating rate of 10 ℃/min in air, preserving heat for 2 hours, and cooling to room temperature at a cooling rate of 2 ℃/min for oxidation.
(11) Coating the surface of the material obtained in the step (10) with thin silver paste with the thickness of 0.05mm, heating to 850 ℃, preserving heat for 30min, sintering silver, and cooling to room temperature.
(12) And (3) sequentially polishing the silver electrode of the silver-burned material with 8000-mesh and 10000-mesh sand paper until the surface is smooth, and displaying a clear figure.
(13) And (3) putting the polished material into silicone oil, and polarizing for 25 minutes under the condition that the polarizing electric field is 4.2kV/mm and the polarizing temperature is 30 ℃ to obtain the barium titanate-based lead-free piezoelectric ceramic.
Piezoelectric performance tests were conducted on the barium titanate-based leadless piezoelectric ceramics prepared in examples 1 to 7 and comparative examples 1 to 2.
Fig. 1 (a) and 1 (d) show XRD patterns of barium titanate-based lead-free piezoelectric ceramics obtained in examples 1 to 7 and comparative examples 1 to 2 under different conditions using a conventional solid phase method at 2θ=18 to 70 °. From the figure, it can be seen that the characteristic peak-to-average of all the examples is identical to that of the standard card (JCPLS card 05-0626) of tetragonal barium titanate, indicating that the above barium titanate-based piezoelectric ceramic has a tetragonal perovskite structure. The XRD pattern shows that the sample has no impurity phase, sharp peak shape, high peak strength and high crystallinity.
As can be seen from (b) and (c) in fig. 1, the peak positions of examples 1 to 5 are shifted to a higher angle as a whole than comparative example 1, indicating that internal defects of the barium titanate-based lead-free piezoelectric ceramic, that is, oxygen vacancies and titanium vacancies, are reduced after the oxidation treatment. The overall peak positions of examples 1-3 shift to high angles, indicating a reduction in charge defects of the samples; the peak positions of examples 3 to 5 are shifted to a low angle overall, indicating an increase in charge defects of the samples. As can be seen from fig. 1 (e) and 1 (f), the peaks of comparative example 2, example 3, example 6 and example 7 are shifted to high angles as the Ti/Ba ratio is reduced.
Fig. 2 (a) to (i) are scanning electron microscope pictures of barium titanate-based lead-free piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2, respectively. As can be seen from FIGS. 2 (a) to (i), the average grain size and the relative density of comparative example 1 were smaller than those of examples 1 to 7, indicating that defects such as voids, microcracks, and charge defects inside the sample could be reduced after the oxidation treatment. The grain sizes of examples 1 to 5 were gradually increased. As can be seen from fig. 2 (d) and (g) to (i), as the Ti/Ba ratio increases, the grains of the ceramic become smaller and then larger. The piezoelectric constant of piezoelectric ceramics is closely related to grain size and defects: when the grain size is smaller, the piezoelectric constant increases as the grain size increases; when the grain size is excessively large, the piezoelectric constant decreases with an increase in the grain size due to the grain boundary effect or the like.
The grain sizes of the barium titanate-based lead-free piezoelectric ceramics of examples 1 to 5 and comparative example 1 are shown in fig. 3 (a), and it can be seen that the grain sizes of examples 1 to 5 are gradually increased and are all larger than comparative example 1, which is consistent with the results shown in fig. 2. Fig. 3 (b) shows average grain sizes of example 3, examples 6 to 7 and comparative example 2, in which the grains of the ceramics become smaller and then larger as the Ti/Ba ratio increases.
It can be seen from fig. 4 (a) that the relative densities of examples 3 to 5 gradually decrease as the relative densities of examples 1 to 3 can be seen to gradually increase, and are all greater than comparative example 1. The grain sizes of examples 4 and 5 were larger and the relative densities were smaller than in example 3, because the interactions between grain boundaries suppressed densification of the samples. The average grain size and the relative density of comparative example 1 are smaller than those of examples 1 to 5, showing that the oxidation step can effectively reduce the defects such as voids, microcracks, and charge defects inside the piezoelectric ceramic. As can be seen from fig. 4 (b), the relative density of example 3 is greater than that of examples 6 to 7 and comparative example 2, indicating that defects in the ceramic decrease and then increase with increasing Ti/Ba ratio.
Fig. 5 shows the hysteresis loops (P-E) of the barium titanate-based leadless piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2 at an electric field of 40kV/cm, from which it can be seen that each sample has a saturated hysteresis loop, indicating that the sample has good performance. The closed loop area of the hysteresis loop is generally proportional to the energy loss of the ferroelectric material, which is used to overcome the spontaneous polarization change direction and to overcome the frictional resistance of impurities and lattice defects to domain walls, and the hysteresis loop of the polycrystalline piezoelectric ceramic material with more defects and complex stress is wider. As can be seen from (a) of fig. 5, the closed loop area of the hysteresis loop of comparative example 1 is larger than that of examples 1 to 5, indicating that comparative example 1 has a larger number of defects than examples 1 to 5. The minimum closed loop area of example 3 indicates that the piezoelectric ceramic of example 3 has a complete internal structure and a small number of charge defects. Fig. 4 (b) shows that the maximum polarization and the remnant polarization of example 3 are both greater than those of examples 6 to 7 and comparative example 2, indicating that the performance of the barium titanate piezoelectric ceramic of example 3 is higher.
Fig. 6 shows saturated polarization (Pmax), residual polarization (Pr) and coercive field Ec values of the barium titanate-based lead-free piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2. As can be seen from fig. (a), the saturation polarization and the remnant polarization of comparative example 1 are both smaller than those of examples 1 to 5, indicating that the oxidation step can reduce the internal charge defects of the piezoelectric ceramic sample, which is consistent with the conclusion of fig. 1. The saturated polarization intensity and the remnant polarization intensity of examples 1 to 3 gradually increased, and the saturated polarization intensity and the remnant polarization intensity of examples 3 to 5 gradually decreased. This is because, from examples 1 to 3, as the sintering temperature increases, the charge defects in the sample decrease, the number of defect dipoles formed by the charge defects are reduced, the number of defect dipoles pinned in the vicinity of domain walls decreases, and the resistance against domain wall movement decreases, so that the polarization weakening of the sample decreases. On the other hand, the decrease of the defective dipole leads to a decrease of the interaction between the defective dipole and the electric domain, an increase of the ordering of the sample, and an increase of the remnant polarization. From example 3 to example 5, as the sintering temperature increases, a large number of defects such as oxygen vacancies are generated at high temperature, and these defects interact to form defect dipoles that block domain wall movement and disorder the electric domains, resulting in a decrease in remnant polarization. As can be seen from fig. 6 (b), as the Ti/Ba ratio increases, the saturated polarization intensity and the remnant polarization intensity increase and decrease, and as a result of the graph (a) and the above analysis, the performance of example 3 is the best. The saturated polarization intensity of example 3 was 22.3279. Mu.C/cm 2, and the residual polarization intensity was 9.7078. Mu.C/cm 2.
The coercive field E C of each of examples 1 to 5 was smaller than that of comparative example 1, indicating that the piezoelectric ceramics obtained by the oxidation treatment had a smaller number of overall charge defects. The coercive field of examples 1 to 3 gradually decreases, and the coercive field of example 3 is smaller than those of examples 6 to 7 and comparative example 2. The lower the coercive field, the easier polarization is to do. Because the defective dipole is pinned near the domain wall of the domain, steering of the domain is hindered, and resistance to polarization is increased.
FIG. 7 shows dielectric constants of barium titanate lead-free piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2 at a frequency of 1 kHz. As can be seen from fig. 7, the samples of examples 1 to 7 and comparative examples 1 to 2 have unique peaks in the relative dielectric constant in the range of 25 to 200 c, which represent the transition of the samples from the paraelectric phase to the ferroelectric phase. Compared with comparative example 1, the relative dielectric constants of examples 1 to 5 are all significantly improved, which means that the oxidation treatment can lead to larger crystal grains, increased density and fewer charge defects of the prepared piezoelectric ceramics, which is consistent with the analysis result of fig. 1. For example 3, examples 6 to 7 and comparative example 2, which were similarly oxidized but have different contents of TiO 2, the maximum dielectric constant of example 3 and the corresponding temperature at that value were the largest, indicating that as the Ti/Ba ratio was increased, the maximum dielectric constant tended to increase first and then decrease, and the curie temperature change was uniform.
The respective performance parameters of the barium titanate-based lead-free piezoelectric ceramics of examples 1 to 7 and comparative examples 1 to 2 are shown in table 1 below.
Table 1 shows the performance parameters of the barium titanate-based leadless piezoelectric ceramics prepared in examples 1 to 7 and comparative examples 1 to 2
As can be seen from table 1, the dielectric loss of comparative example 1 is greater than that of examples 1 to 5, indicating that the oxidation step can reduce the charge defects inside the sample. In the same manner, in comparison with examples 3, examples 6 to 7 and comparative example 2, which were subjected to oxidation treatment but have different Ti/Ba ratios, the dielectric loss of example 3 was smaller than that of examples 6 to 7 and comparative example 2, the relative dielectric constant of example 3 was 23889, the tan delta was 1.41%, the dielectric loss was lowest, the piezoelectric ceramic was most dense, indicating the least charge defect, and the performance was optimal.
The relationship between the piezoelectric coefficient d 33 and the relative dielectric constant ε r and the remnant polarization P r can be as follows:
d33＝2Q33εrPr
Wherein Q 33 is the electrostriction coefficient, which is related to the ordered arrangement of cations and can be generally regarded as invariant.
Fig. 8 shows the products of the piezoelectric coefficients d 33, the relative dielectric constants epsilon r, and the residual polarization intensities P r of the barium titanate-based leadless piezoelectric ceramics prepared in examples 1 to 7 and comparative examples 1 to 2. As can be seen from the figure. D 33 and ε rPr are highest for example 3, indicating the best performance.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. The preparation method of the barium titanate-based leadless piezoelectric ceramic is characterized by comprising the following steps of:
Weighing raw materials, and pre-sintering to prepare a precursor;
granulating and molding the precursor to prepare a ceramic blank;
Performing glue discharging, sintering, annealing, oxidation, silver burning and polarization on the ceramic blank to prepare the barium titanate-based leadless piezoelectric ceramic;
Wherein the raw materials comprise BaCO 3 and TiO 2; the general formula of the barium titanate-based leadless piezoelectric ceramic is BaTiO 3·xTiO2, and x is more than 0 and less than or equal to 0.005;
the oxidation comprises the following steps: heating the ceramic body to 1250-1300 ℃, preserving heat for 2-4 hours, and cooling to room temperature;
The presintering comprises the following steps: heating the raw materials to 1000-1200 ℃, and preserving heat for 2-4 hours;
The glue discharging comprises the following steps: heating the ceramic blank to 600-650 ℃, and preserving heat for 3-4 hours;
the sintering comprises the following steps: heating the material subjected to glue discharging to 1300-1400 ℃, and preserving heat for 3-4 hours;
The annealing includes the steps of: heating the sintered material to 1000-1100 ℃, and preserving heat for 2.5-3 hours;
The silver burning comprises the following steps: and heating the oxidized material to 800-850 ℃, and preserving heat for 30-50 min.
2. The method for producing a barium titanate-based lead-free piezoelectric ceramic according to claim 1, wherein in the oxidizing step, a temperature rising rate is 5 ℃/min to 10 ℃/min.
3. The method for producing a barium titanate-based lead-free piezoelectric ceramic according to claim 1, wherein in the oxidizing step, the cooling rate is 2 ℃/min to 5 ℃/min.
4. The method for preparing barium titanate-based lead-free piezoelectric ceramic according to claim 1, further comprising the steps of mixing, first pulverizing and first drying the raw materials before the step of pre-sintering.
5. The method for preparing barium titanate-based lead-free piezoelectric ceramic according to claim 1, further comprising the steps of pulverizing the precursor a second time and drying the precursor a second time before the granulating step.
6. The method of preparing a barium titanate-based lead-free piezoelectric ceramic according to claim 1, further comprising a step of polishing the sintered material before the annealing step, wherein the polishing conditions include: and polishing by adopting sand paper with 1200-8000 meshes.
7. The method for preparing barium titanate-based leadless piezoelectric ceramics according to any one of claims 1 to 6, wherein the step of firing silver further comprises, before heating, coating a thin silver paste with a thickness of 0.03mm to 0.05mm on the surface of the oxidized material.
8. The method for preparing a barium titanate-based lead-free piezoelectric ceramic according to any one of claims 1 to 6, wherein the polarization conditions include: the polarization electric field is 4.2 kV/mm-4.5/kV/mm, the polarization temperature is 28-32 ℃, and the polarization time is 25-40 min.
9. A barium titanate-based lead-free piezoelectric ceramic, characterized in that it is prepared by the method for preparing the barium titanate-based lead-free piezoelectric ceramic according to any one of claims 1 to 8.
10. An electronic component comprising the barium titanate-based lead-free piezoelectric ceramic of claim 9.
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