CN107573034B - Preparation method of lead-free piezoelectric ceramic - Google Patents
Preparation method of lead-free piezoelectric ceramic Download PDFInfo
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Abstract
The invention provides a lead-free piezoelectric ceramic and a preparation method thereof. The preparation method comprises the following steps: (1) preparation of Bi3Zr2TiNO11A nanopowder; (2) with BaCl2、Na2CO3、Y2O3、Cs2CO3、TiB2、SrCO3、Bi3Zr2TiNO11The nanometer powder is taken as a raw material, absolute ethyl alcohol is taken as a ball milling medium, and the ball milling is carried out to obtain powder; (3) drying the slurry, adding a polyvinyl alcohol aqueous solution as a binder, standing for 24h, sieving with a sieve of 150 meshes and 200 meshes, and tabletting the obtained powder to form a blank; (4) placing the blank into a muffle furnace for plastic removal, and sintering at high temperature to prepare ceramic after plastic removal; (5) polishing the surface of the sintered ceramic, plating silver electrode, then putting into silicon oil, and polarizing. The piezoelectric ceramic material has excellent performance and high mechanical quality factor.
Description
Technical Field
The invention relates to the field of piezoelectric ceramic materials, in particular to a preparation method of lead-free piezoelectric ceramic.
Background
The piezoelectric ceramic is a functional ceramic material capable of realizing interconversion of mechanical energy and electric energy. Compared with piezoelectric single crystal materials, the piezoelectric single crystal material has the advantages of high electromechanical coupling coefficient, good adjustability of piezoelectric performance, stable chemical property, easy preparation, capability of preparing products in various shapes, sizes and any polarization directions, low price and the like, and is widely applied to high and new technical fields of satellite broadcasting, electronic equipment, biology, aerospace and the like.
However, the piezoelectric ceramic bodies used at present are mainly lead-based piezoelectric ceramics in which PbO (or Pb) is contained3O4) The content of (A) is about 70% of the total mass of the raw materials. Due to PbO and Pb3O4The volatility of lead-containing compounds at high temperature causes great harm to human health and ecological environment in the processes of production, use and waste of the ceramics. The cost required is also high if a pollution-free treatment is applied to the recycling of lead-containing ceramic devices. On the other hand, volatilization of PbO also causes the stoichiometric ratio of the ceramic to deviate from the stoichiometric ratio in the formulation, resulting in reduced product consistency and repeatability. Therefore, the research and development of the lead-free piezoelectric ceramic which is environment-friendly becomes an urgent and practical topic, the performance of the lead-free piezoelectric ceramic is improved to a great extent by methods such as doping, substitution modification and improvement of the ceramic preparation process, and a plurality of performances reach the applicable level. However, compared with lead-based piezoelectric ceramics, the lead-free piezoelectric ceramics have better performanceThe large difference is far from reaching the level of replacing lead-based piezoelectric ceramics. Therefore, in order to expand the application range of the lead-free piezoelectric ceramics, further improvement of the performance, particularly, the electromechanical coupling coefficient, the piezoelectric performance, and the like is required. Among a plurality of leadless piezoelectric ceramics, the A-site composite perovskite ceramic Bi0 .5Na0 .5TiO3(BNT) is considered to be the most substituted candidate for lead-based piezoelectric ceramics due to its excellent electrical properties. However, pure BNT ceramics have large coercive field strength (E c ≈ 7.3 k V/mm) and high leakage current, resulting in pure Bi0 .5Na0 .5TiO3The ceramic polarization is difficult, the piezoelectric constant d33 is approximately equal to 73pC/N, the requirements of practical application cannot be met, the operation process is complex, the prepared piezoelectric ceramic material has poor performance, and the application of the pure BNT ceramic in practice is limited by narrow sintering temperature zone, poor compactness and unstable physicochemical properties.
The advent and development of nanotechnology has provided a good opportunity and platform for the improvement of lead-free piezoelectric ceramics because nanomaterials have novel physical and chemical properties that are different from their bulk. Research shows that if the size of the raw material of the lead-free piezoelectric ceramic is in the nanometer level, the ceramic performance can be greatly improved by controlling the parameters of 1 or more components in the lead-free piezoelectric ceramic nanometer powder (raw material), such as composition, size, shape, uniformity and the like.
Disclosure of Invention
The technical problem to be solved is as follows: the invention aims to provide a lead-free piezoelectric ceramic, which can effectively solve the problems of complex production process, difficult sintering and poor piezoelectric ceramic performance, and can not meet the requirements in practical application. And further improve its performance, in particular the electromechanical coupling coefficient, the piezoelectric properties and the mechanical quality factor.
The technical scheme is as follows: a preparation method of lead-free piezoelectric ceramics comprises the following steps:
(1) with BiCO3、NaNO3 、TiO2And ZrO2Powder of Bi according to formula3Zr2TiNO11，BiCO3、NaNO3 、TiO2And ZrO220 parts of mixed raw materials with the molar ratio of 3:1:1:2, putting the powder into a ball mill for ball milling for 3-5h, uniformly mixing, adding 500ml of KOH solution with the concentration of 10%, stirring for 40-60min to uniformly mix the solution, transferring the mixed solution into a hydrothermal kettle, heating the mixed solution to 190 ℃ for 250 ℃, preserving the temperature for 10-14h, filtering, washing and drying precipitates generated in the reaction to obtain Bi3Zr2TiNO11A nanopowder;
(2) with BaCl2、Na2CO3、Y2O3、Cs2CO3、TiB2、SrCO3And step (1) and pre-sintering the Bi3Zr2TiNO11Powder as raw material, according to BaCl2：Na2CO3：Y2O3：Cs2CO3：TiB2：SrCO3：Bi3Zr2TiNO11In a molar ratio of 5: 3:1: 2: 1:1: 5, weighing the ingredients according to the stoichiometric ratio, and performing ball milling for 10-15 hours for one time by taking zirconium dioxide as a grinding ball and absolute ethyl alcohol as a medium in a rolling ball milling manner;
(3) drying the slurry ball-milled in the step (2), adding 6g of 8% polyvinyl alcohol aqueous solution serving as an adhesive into every 100g of powder, standing for 24h, sieving with a sieve of 200 meshes at 150 meshes, tabletting the obtained powder to form a blank, wherein the molding pressure is 330MPa at 200 meshes, and the diameter of the blank is 13 mm;
(4) placing the blank into a corundum crucible, then placing the corundum crucible into a muffle furnace for plastic removal, wherein the plastic removal temperature is 500-750 ℃, and the plastic removal time is 1-5h, so as to obtain a biscuit; placing the biscuit with the plastic discharged into a corundum crucible, burying the biscuit with powder with the same weight ratio, and sintering the biscuit in a muffle furnace at the sintering temperature of 1100-1250 ℃ for 2-6h to obtain the Y and B doped BaCsTiSrO3- Bi3Zr2TiNO11Lead-free piezoelectric ceramics;
(5) polishing and smoothing the surface of the lead-free piezoelectric ceramic prepared in the step (4), coating conductive silver paste, and calcining at the temperature of 530 ℃ and 700 ℃ in a sintering furnace for 30-60min to form a silver electrode on the surface; and (3) putting the lead-free piezoelectric ceramic of the silver electrode in silicon oil, polarizing for 20-40min by using an electric field of 3-6kV/mm, and standing for 24h to obtain the lead-free piezoelectric ceramic material.
Further, the preparation method of the lead-free piezoelectric ceramic comprises the steps of (1) ball milling for 4-5h by a ball mill, stirring the mixed solution for 45-55min, heating the mixed solution to 210-230 ℃ and preserving heat for 11-12 h.
Further, in the preparation method of the lead-free piezoelectric ceramic, a ball milling mode is adopted in the step (2), and ball milling is carried out for 12-14 hours at one time.
Furthermore, in the preparation method of the lead-free piezoelectric ceramic, in the step (3), the mesh number of the sieve is 160-.
Further, in the preparation method of the lead-free piezoelectric ceramic, in the step (4), the plastic discharging temperature is 600-700 ℃, the plastic discharging time is 2-4 hours, the sintering temperature is 1150-1200 ℃, and the sintering time is 3-5 hours.
Further, in the preparation method of the lead-free piezoelectric ceramic, in the step (5), the ceramic is calcined in a sintering furnace at the temperature of 600 ℃ and 650 ℃ for 35-50min, and polarized by an electric field of 4-5kV/mm for 25-35 min.
Has the advantages that: the invention designs and synthesizes yttrium (Y) and boron (B) co-doped BaCsTiSrO for the first time3- Bi3Zr2TiNO11The lead-free piezoelectric ceramic is systematically researched and tested for the electrical properties, the coercive field strength and the leakage current of the piezoelectric ceramic can be effectively reduced, the polarizability is improved, and the method is simple, easy to produce and prepare and has very high practical application value. After testing, the lead-free piezoelectric ceramic has excellent electrical properties: piezoelectric constant d33427-473pC/N, planar electromechanical coupling coefficient kp0.39-0.46, mechanical quality factor Qm122, 133.
Detailed Description
Example 1
A preparation method of lead-free piezoelectric ceramics comprises the following steps: (1) with BiCO3、NaNO3 、TiO2And ZrO2Powder of Bi according to formula3Zr2TiNO11，BiCO3、NaNO3 、TiO2And ZrO220 parts of mixed raw materials with the molar ratio of 3:1:1:2, putting the powder into a ball mill, ball-milling for 3 hours, uniformly mixing, adding 500ml of KOH solution with the concentration of 10%, stirring for 40 minutes to uniformly mix the solution, transferring the mixed solution into a hydrothermal kettle, heating the mixed solution to 190 ℃, preserving heat for 10 hours, filtering, washing and drying precipitates generated in the reaction to obtain Bi3Zr2TiNO11A nanopowder; (2) with BaCl2、Na2CO3、Y2O3、Cs2CO3、TiB2、SrCO3And step (1) and pre-sintering the Bi3Zr2TiNO11Powder as raw material, according to BaCl2：Na2CO3：Y2O3：Cs2CO3：TiB2：SrCO3：Bi3Zr2TiNO11In a molar ratio of 5: 3:1: 2: 1:1: 5, weighing the ingredients according to the stoichiometric ratio, and performing ball milling for 15 hours once by using zirconium dioxide as a grinding ball and absolute ethyl alcohol as a medium in a rolling ball milling manner; (3) drying the slurry ball-milled in the step (2), adding 6g of 8% polyvinyl alcohol aqueous solution serving as an adhesive into every 100g of powder, standing for 24h, sieving by a 150-mesh sieve, and tabletting the obtained powder into a blank, wherein the molding pressure is 200MPa, and the diameter of the blank is 13 mm; (4) placing the blank into a corundum crucible, and then placing the corundum crucible into a muffle furnace for plastic removal, wherein the plastic removal temperature is 500 ℃, and the plastic removal time is 1h, so that a biscuit is formed; putting the biscuit with the plastic discharged into a corundum crucible, burying the biscuit with powder with the same weight ratio, and sintering the biscuit in a muffle furnace at the sintering temperature of 1100 ℃ for 2 hours to obtain Y and B doped BaCsTiSrO3- Bi3Zr2TiNO1Lead-free piezoelectric ceramics; (5) polishing and smoothing the surface of the lead-free piezoelectric ceramic prepared in the step (4), coating conductive silver paste, and calcining in a sintering furnace at 700 ℃ for 30min to form a silver electrode on the surface; and (3) putting the lead-free piezoelectric ceramic of the silver electrode in silicone oil, polarizing for 20min by using an electric field of 3kV/mm, and standing for 24h to obtain the lead-free piezoelectric ceramic material.
Example 2
A preparation method of lead-free piezoelectric ceramics comprises the following steps: (1) with BiCO3、NaNO3 、TiO2And ZrO2Powder of Bi according to formula3Zr2TiNO11，BiCO3、NaNO3 、TiO2And ZrO220 parts of mixed raw materials with the molar ratio of 3:1:1:2, putting the powder into a ball mill for ball milling for 5 hours, uniformly mixing, adding 500ml of KOH solution with the concentration of 10%, stirring for 40-60 minutes to uniformly mix the solution, transferring the mixed solution into a hydrothermal kettle, heating the mixed solution to 190 ℃ and 250 ℃, preserving the temperature for 14 hours, filtering, washing and drying precipitates generated in the reaction to obtain Bi3Zr2TiNO11A nanopowder; (2) with BaCl2、Na2CO3、Y2O3、Cs2CO3、TiB2、SrCO3And step (1) and pre-sintering the Bi3Zr2TiNO11Powder as raw material, according to BaCl2：Na2CO3：Y2O3：Cs2CO3：TiB2：SrCO3：Bi3Zr2TiNO11In a molar ratio of 5: 3:1: 2: 1:1: 5, weighing the ingredients according to the stoichiometric ratio, and performing ball milling for 10 hours at one time by using zirconium dioxide as a grinding ball and absolute ethyl alcohol as a medium in a rolling ball milling manner; (3) drying the slurry ball-milled in the step (2), adding 6g of 8% polyvinyl alcohol aqueous solution serving as an adhesive into every 100g of powder, standing for 24h, sieving by a 200-mesh sieve, tabletting the obtained powder to form a blank, wherein the molding pressure is 200MPa and 330MPa, and the diameter of the blank is 13 mm; (4) placing the blank into a corundum crucible, and then placing the corundum crucible into a muffle furnace for plastic removal, wherein the plastic removal temperature is 750 ℃, and the plastic removal time is 5 hours, so as to obtain a biscuit; putting the biscuit with the plastic discharged into a corundum crucible, burying the biscuit with powder with the same weight ratio, and sintering the biscuit in a muffle furnace at the sintering temperature of 1100 ℃ for 6 hours to obtain Y and B doped BaCsTiSrO3- Bi3Zr2TiNO1Lead-free piezoelectric ceramics; (5) polishing and smoothing the surface of the lead-free piezoelectric ceramic prepared in the step (4)Coating conductive silver paste, calcining for 60min at 530 ℃ in a sintering furnace, and forming a silver electrode on the surface; and (3) putting the lead-free piezoelectric ceramic of the silver electrode in silicone oil, polarizing for 20min by using an electric field of 6kV/mm, and standing for 24h to obtain the lead-free piezoelectric ceramic material.
Example 3
A preparation method of lead-free piezoelectric ceramics comprises the following steps: (1) with BiCO3、NaNO3 、TiO2And ZrO2Powder of Bi according to formula3Zr2TiNO11，BiCO3、NaNO3 、TiO2And ZrO220 parts of mixed raw materials with the molar ratio of 3:1:1:2, putting the powder into a ball mill for ball milling for 4 hours, uniformly mixing, adding 500ml of KOH solution with the concentration of 10%, stirring for 45 minutes to uniformly mix the solution, transferring the mixed solution into a hydrothermal kettle, heating the mixed solution to 210 ℃, preserving heat for 12 hours, filtering, washing and drying precipitates generated in the reaction to obtain Bi3Zr2TiNO11A nanopowder; (2) with BaCl2、Na2CO3、Y2O3、Cs2CO3、TiB2、SrCO3And step (1) and pre-sintering the Bi3Zr2TiNO11Powder as raw material, according to BaCl2：Na2CO3：Y2O3：Cs2CO3：TiB2：SrCO3：Bi3Zr2TiNO11In a molar ratio of 5: 3:1: 2: 1:1: 5, weighing the ingredients according to the stoichiometric ratio, and performing ball milling for 12 hours once by using zirconium dioxide as a grinding ball and absolute ethyl alcohol as a medium in a rolling ball milling manner; (3) drying the slurry ball-milled in the step (2), adding 6g of 8% polyvinyl alcohol aqueous solution serving as an adhesive into every 100g of powder, standing for 24h, sieving by a 160-mesh sieve, and tabletting the obtained powder into a blank, wherein the molding pressure is 250MPa, and the diameter of the blank is 13 mm; (4) placing the blank into a corundum crucible, and then placing the corundum crucible into a muffle furnace for plastic removal, wherein the plastic removal temperature is 600 ℃, and the plastic removal time is 2 hours, so that a biscuit blank is formed; placing the biscuit with the discharged plastic into a corundum crucible, burying the biscuit with powder with the same weight ratio, and placing the biscuitSintering in a muffle furnace at 1200 ℃ for 3h to obtain Y and B doped BaCsTiSrO3- Bi3Zr2TiNO1Lead-free piezoelectric ceramics; (5) polishing and smoothing the surface of the lead-free piezoelectric ceramic prepared in the step (4), coating conductive silver paste, and calcining for 35min at 600 ℃ in a sintering furnace to form a silver electrode on the surface; and (3) putting the lead-free piezoelectric ceramic of the silver electrode in silicone oil, polarizing for 25min by using an electric field of 4kV/mm, and standing for 24h to obtain the lead-free piezoelectric ceramic material.
Example 4
A preparation method of lead-free piezoelectric ceramics comprises the following steps: (1) with BiCO3、NaNO3 、TiO2And ZrO2Powder of Bi according to formula3Zr2TiNO11，BiCO3、NaNO3 、TiO2And ZrO220 parts of mixed raw materials with the molar ratio of 3:1:1:2, putting the powder into a ball mill, ball-milling for 5 hours, uniformly mixing, adding 500ml of KOH solution with the concentration of 10%, stirring for 55 minutes to uniformly mix the solution, transferring the mixed solution into a hydrothermal kettle, heating the mixed solution to 230 ℃, preserving heat for 12 hours, filtering, washing and drying precipitates generated in the reaction to obtain Bi3Zr2TiNO11A nanopowder; (2) with BaCl2、Na2CO3、Y2O3、Cs2CO3、TiB2、SrCO3And step (1) and pre-sintering the Bi3Zr2TiNO11Powder as raw material, according to BaCl2：Na2CO3：Y2O3：Cs2CO3：TiB2：SrCO3：Bi3Zr2TiNO11In a molar ratio of 5: 3:1: 2: 1:1: 5, weighing the ingredients according to the stoichiometric ratio, and performing ball milling for 14 hours once by using zirconium dioxide as a grinding ball and absolute ethyl alcohol as a medium in a rolling ball milling manner; (3) drying the slurry ball-milled in the step (2), adding 6g of polyvinyl alcohol aqueous solution with the mass concentration of 8% into every 100g of powder as an adhesive, standing for 24h, sieving by a 180-mesh sieve, tabletting the obtained powder into a blank, and molding the blankThe pressure is 300MPa, and the diameter of the blank is 13 mm; (4) placing the blank into a corundum crucible, and then placing the corundum crucible into a muffle furnace for plastic removal, wherein the plastic removal temperature is 700 ℃, and the plastic removal time is 4 hours, so that a biscuit is formed; putting the biscuit with the discharged plastic into a corundum crucible, burying the biscuit with powder with the same weight ratio, and sintering the biscuit in a muffle furnace at 1150 ℃ for 3 hours to obtain Y and B doped BaCsTiSrO3- Bi3Zr2TiNO1Lead-free piezoelectric ceramics; (5) polishing and smoothing the surface of the lead-free piezoelectric ceramic prepared in the step (4), coating conductive silver paste, and calcining for 50min at 650 ℃ in a sintering furnace to form a silver electrode on the surface; and (3) putting the lead-free piezoelectric ceramic of the silver electrode in silicone oil, polarizing for 50min by using an electric field of 5kV/mm, and standing for 24h to obtain the lead-free piezoelectric ceramic material.
Example 5
A preparation method of lead-free piezoelectric ceramics comprises the following steps: (1) with BiCO3、NaNO3 、TiO2And ZrO2Powder of Bi according to formula3Zr2TiNO11，BiCO3、NaNO3 、TiO2And ZrO220 parts of mixed raw materials with the molar ratio of 3:1:1:2, putting the powder into a ball mill for ball milling for 4 hours, uniformly mixing, adding 500ml of KOH solution with the concentration of 10%, stirring for 50 minutes to uniformly mix the solution, transferring the mixed solution into a hydrothermal kettle, heating the mixed solution to 220 ℃, preserving heat for 12 hours, filtering, washing and drying precipitates generated in the reaction to obtain Bi3Zr2TiNO11A nanopowder; (2) with BaCl2、Na2CO3、Y2O3、Cs2CO3、TiB2、SrCO3And step (1) and pre-sintering the Bi3Zr2TiNO11Powder as raw material, according to BaCl2：Na2CO3：Y2O3：Cs2CO3：TiB2：SrCO3：Bi3Zr2TiNO11In a molar ratio of 5: 3:1: 2: 1:1: 5, taking zirconium dioxide as grinding ball and absolute ethyl alcohol as medium, adopting rollingPerforming ball milling for 13 hours at one time in a ball milling mode; (3) drying the slurry ball-milled in the step (2), adding 6g of 8% polyvinyl alcohol aqueous solution serving as an adhesive into every 100g of powder, standing for 24h, sieving by a 170-mesh sieve, and tabletting the obtained powder into a blank, wherein the molding pressure is 275MPa, and the diameter of the blank is 13 mm; (4) placing the blank into a corundum crucible, and then placing the corundum crucible into a muffle furnace for plastic removal, wherein the plastic removal temperature is 650 ℃, and the plastic removal time is 3 hours, so that a biscuit is formed; putting the biscuit with the plastic discharged into a corundum crucible, burying the biscuit with powder with the same weight ratio, and sintering the biscuit in a muffle furnace at 1175 ℃ for 4 hours to obtain Y and B doped BaCsTiSrO3- Bi3Zr2TiNO1Lead-free piezoelectric ceramics; (5) polishing and smoothing the surface of the lead-free piezoelectric ceramic prepared in the step (4), coating conductive silver paste, and calcining at 625 ℃ in a sintering furnace for 40min to form a silver electrode on the surface; and (3) putting the lead-free piezoelectric ceramic of the silver electrode in silicone oil, polarizing for 30min by using an electric field of 4kV/mm, and standing for 24h to obtain the lead-free piezoelectric ceramic material.
Comparative example 1
A preparation method of lead-free piezoelectric ceramics comprises the following steps: (1) with BaCl2、Na2CO3、Y2O3、Cs2CO3、TiB2、SrCO3、BiCO3、NaNO3 、TiO2And ZrO2Powder as raw material, according to BaCl2：Na2CO3：Y2O3：Cs2CO3：TiB2：SrCO3：BiCO3：NaNO3 ：TiO2：ZrO2In a molar ratio of 5: 3:1: 2: 1:1: 9: 3: 3: 6, weighing the ingredients according to the stoichiometric ratio, and performing ball milling for 15 hours once by using zirconium dioxide as a grinding ball and absolute ethyl alcohol as a medium in a rolling ball milling manner; (2) drying the slurry ball-milled in the step (1), adding 6g of 8% polyvinyl alcohol aqueous solution serving as an adhesive into every 100g of powder, standing for 24h, sieving by a 150-mesh sieve, and tabletting the obtained powder into a blank, wherein the molding pressure is 200MPa, and the diameter of the blank is 13 mm; (3) placing the blank into a corundum cruciblePlacing the crucible into a muffle furnace for plastic removal, wherein the plastic removal temperature is 500 ℃, and the plastic removal time is 1h, so as to obtain a biscuit; putting the biscuit with the plastic discharged into a corundum crucible, burying the biscuit with powder with the same weight ratio, and sintering the biscuit in a muffle furnace at the sintering temperature of 1100 ℃ for 2 hours to obtain Y and B doped BaCsTiSrO3- Bi3Zr2TiNO1Lead-free piezoelectric ceramics; (4) polishing and smoothing the surface of the lead-free piezoelectric ceramic prepared in the step (3), coating conductive silver paste, and calcining in a sintering furnace at 700 ℃ for 30min to form a silver electrode on the surface; and (3) putting the lead-free piezoelectric ceramic of the silver electrode in silicone oil, polarizing for 20min by using an electric field of 3kV/mm, and standing for 24h to obtain the lead-free piezoelectric ceramic material.
Comparative example 2
A preparation method of lead-free piezoelectric ceramics comprises the following steps: (1) with BiCO3、NaNO3 、TiO2And ZrO2Powder of Bi according to formula3Zr2TiNO11，BiCO3、NaNO3 、TiO2And ZrO220 parts of mixed raw materials with the molar ratio of 3:1:1:2, putting the powder into a ball mill for ball milling for 5 hours, uniformly mixing, adding 500ml of KOH solution with the concentration of 10%, stirring for 40-60 minutes to uniformly mix the solution, transferring the mixed solution into a hydrothermal kettle, heating the mixed solution to 190 ℃ and 250 ℃, preserving the temperature for 14 hours, filtering, washing and drying precipitates generated in the reaction to obtain Bi3Zr2TiNO11A nanopowder; (2) with BaCl2、Na2CO3、Cs2CO3、TiB2、SrCO3And step (1) and pre-sintering the Bi3Zr2TiNO11Powder as raw material, according to BaCl2：Na2CO3：Cs2CO3：TiB2：SrCO3：Bi3Zr2TiNO11In a molar ratio of 5: 3: 2: 1:1: 5, weighing the ingredients according to the stoichiometric ratio, and performing ball milling for 10 hours at one time by using zirconium dioxide as a grinding ball and absolute ethyl alcohol as a medium in a rolling ball milling manner; (3) drying the slurry ball-milled in the step (2), and adding 6g of concentrated powder into every 100g of powderTaking a polyvinyl alcohol aqueous solution with the degree of 8% as an adhesive, standing for 24h, sieving by a 200-mesh sieve, tabletting the obtained powder to form a blank, wherein the molding pressure is 200-330MPa, and the diameter of the blank is 13 mm; (4) placing the blank into a corundum crucible, and then placing the corundum crucible into a muffle furnace for plastic removal, wherein the plastic removal temperature is 750 ℃, and the plastic removal time is 5 hours, so as to obtain a biscuit; placing the biscuit with the discharged plastic into a corundum crucible, burying the biscuit with powder with the same weight ratio, and sintering the biscuit in a muffle furnace at the sintering temperature of 1100 ℃ for 6 hours to obtain the BaCsTiSrO doped with only B3- Bi3Zr2TiNO1Lead-free piezoelectric ceramics; (5) polishing and smoothing the surface of the lead-free piezoelectric ceramic prepared in the step (4), coating conductive silver paste, and calcining at 530 ℃ for 60min in a sintering furnace to form a silver electrode on the surface; and (3) putting the lead-free piezoelectric ceramic of the silver electrode in silicone oil, polarizing for 20min by using an electric field of 6kV/mm, and standing for 24h to obtain the lead-free piezoelectric ceramic material.
The performance indexes of the material are shown in the table below, and we can see that the piezoelectric constant of the piezoelectric ceramic can be optimally up to 473pC/N, the electromechanical coupling coefficient is 0.46, and the mechanical quality factor is 133.
TABLE 1 various performance indexes of piezoelectric ceramics
Claims (6)
1. A preparation method of lead-free piezoelectric ceramics is characterized by comprising the following steps:
(1) with BiCO3、NaNO3、TiO2And ZrO2Powder of Bi according to formula3Zr2TiNO11，BiCO3、NaNO3、TiO2And ZrO220 parts of mixed raw materials with the molar ratio of 3:1:1:2, putting the powder into a ball mill for ball milling for 3-5h, uniformly mixing, adding 500ml of KOH solution with the concentration of 10%, stirring for 40-60min to uniformly mix the solution, transferring the mixed solution into a hydrothermal kettle, heating the mixed solution to 190 ℃ for 250 ℃, preserving the temperature for 10-14h, filtering, washing and washing precipitates generated in the reactionAnd drying to obtain Bi3Zr2TiNO11A nanopowder;
(2) with BaCl2、Na2CO3、Y2O3、Cs2CO3、TiB2、SrCO3And Bi pre-sintered in the step (1)3Zr2TiNO11Powder as raw material, according to BaCl2：Na2CO3：Y2O3：Cs2CO3：TiB2：SrCO3：Bi3Zr2TiNO11In a molar ratio of 5: 3:1: 2: 1:1: 5, weighing the ingredients according to the stoichiometric ratio, and performing ball milling for 10-15 hours for one time by taking zirconium dioxide as a grinding ball and absolute ethyl alcohol as a medium in a rolling ball milling manner;
(3) drying the slurry ball-milled in the step (2), adding 6g of 8% polyvinyl alcohol aqueous solution serving as an adhesive into every 100g of powder, standing for 24h, sieving with a sieve of 200 meshes at 150 meshes, tabletting the obtained powder to form a blank, wherein the molding pressure is 330MPa at 200 meshes, and the diameter of the blank is 13 mm;
(4) placing the blank into a corundum crucible, then placing the corundum crucible into a muffle furnace for plastic removal, wherein the plastic removal temperature is 500-750 ℃, and the plastic removal time is 1-5h, so as to obtain a biscuit; placing the biscuit with the plastic discharged into a corundum crucible, burying the biscuit with powder with the same weight ratio, and sintering the biscuit in a muffle furnace at the sintering temperature of 1100-1250 ℃ for 2-6h to obtain the Y and B doped BaCsTiSrO3- Bi3Zr2TiNO1Lead-free piezoelectric ceramics;
(5) polishing and smoothing the surface of the lead-free piezoelectric ceramic prepared in the step (4), coating conductive silver paste, and calcining at the temperature of 530 ℃ and 700 ℃ in a sintering furnace for 30-60min to form a silver electrode on the surface; and (3) putting the lead-free piezoelectric ceramic of the silver electrode in silicon oil, polarizing for 20-40min by using an electric field of 3-6kV/mm, and standing for 24h to obtain the lead-free piezoelectric ceramic material.
2. The method for preparing a lead-free piezoelectric ceramic according to claim 1, characterized in that: the ball milling time of the ball mill in the step (1) is 4-5h, the time for stirring the mixed solution is 45-55min, and the mixed solution is heated to the temperature of 210 ℃ and 230 ℃ and is kept warm for 11-12 h.
3. The method for preparing a lead-free piezoelectric ceramic according to claim 1, characterized in that: and (3) performing ball milling for 12-14h in a ball milling mode in the step (2).
4. The method for preparing a lead-free piezoelectric ceramic according to claim 1, characterized in that: the mesh number in the step (3) is 180 meshes and the molding pressure is 300MPa and 160 meshes.
5. The method for preparing a lead-free piezoelectric ceramic according to claim 1, characterized in that: in the step (4), the plastic discharging temperature is 600-700 ℃, the plastic discharging time is 2-4h, the sintering temperature is 1150-1200 ℃, and the sintering time is 3-5 h.
6. The method for preparing a lead-free piezoelectric ceramic according to claim 1, characterized in that: in the step (5), the material is calcined in a sintering furnace at the temperature of 600-650 ℃ for 35-50min, and polarized by an electric field of 4-5kV/mm for 25-35 min.
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| CN102491752A (en) * | 2011-11-18 | 2012-06-13 | 河南科技大学 | Preparation method of lithium and antimony doped potassium sodium niobate leadless piezoelectric ceramic |
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| CN101037771A (en) * | 2007-02-09 | 2007-09-19 | 上海工程技术大学 | Method for preparing TiC-TiB2 nano-micrometre multiple phase ceramic coating |
| CN101062864A (en) * | 2007-05-28 | 2007-10-31 | 北京科技大学 | Niobic acid sodium potassium lithium radical leadless piezo-electric ceramic and preparation method thereof |
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