CN116444268A - High-voltage performance niobium-antimony-lead zirconate titanate piezoelectric ceramic obtained by high-temperature polarization - Google Patents
High-voltage performance niobium-antimony-lead zirconate titanate piezoelectric ceramic obtained by high-temperature polarization Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 75
- 229910052451 lead zirconate titanate Inorganic materials 0.000 title claims abstract description 51
- 230000010287 polarization Effects 0.000 title claims abstract description 41
- ONYVZOVJANORSJ-UHFFFAOYSA-N [Pb].[Sb].[Nb] Chemical compound [Pb].[Sb].[Nb] ONYVZOVJANORSJ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 28
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
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- 238000003756 stirring Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 238000006073 displacement reaction Methods 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 239000010955 niobium Substances 0.000 abstract 1
- 230000008878 coupling Effects 0.000 description 10
- 238000010168 coupling process Methods 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 10
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 7
- 229910010293 ceramic material Inorganic materials 0.000 description 5
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- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 2
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- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
- C04B35/491—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
- C04B35/493—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT containing also other lead compounds
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- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/3294—Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
Abstract
The invention relates to high-temperature polarization-obtained high-voltage electrical property niobium antimony-lead zirconate titanate piezoelectric ceramic. The niobium-antimony-lead zirconate titanate piezoelectric ceramic comprises the following raw material components in percentage by mole: by Pb (Sb) 1/2 Nb 1/2 ) a Zr b Ti c O 3 On the basis, x mol% ZnO is added, wherein a=0.02 to 0.06, b=0.47 to 0.53, c=0.47 to 0.53 and a+b+c=1, x=0.2 to 0.8. The preparation method of the niobium-antimony-lead zirconate titanate piezoelectric ceramic comprises the following steps: (1) batching; (2) synthesis; (3) fine grinding; (4) granulating; (5) molding; (6) plastic discharge; (7) sintering; (8) electrode coating; (9) high temperature polarization.
Description
Technical Field
The invention relates to a ceramic compound, in particular to a niobium-antimony-lead zirconate titanate piezoelectric ceramic obtained by high-temperature polarization.
Background
Lead zirconate titanate (Pb (Zr) 1-x Ti x )O 3 PZT) piezoelectric ceramics are a class of ceramic materials with excellent piezoelectric constants and electromechanical coupling coefficients, based on PZUltrasonic transducers, hydrophones and the like manufactured by the T piezoelectric ceramics have wide application in a plurality of fields such as military, information communication, aerospace, automotive electronics, medical equipment, petrochemical industry and the like.
When the pure PZT (lead zirconate titanate) ceramic is sintered at high temperature, the melting point of PbO is low, the saturated vapor pressure is high, and the volatilization of lead is easy to generate, so that the components are not easy to control, the stability and the repeatability of the performance are poor, and the application of PZT is greatly limited. Doped PZT piezoelectric ceramics have been shown in the sixties of the twentieth century to reduce the synthesis temperature, lead volatilization, and some properties have been improved. However, binary PZT still does not meet social demands. After that, three-and four-element piezoelectric ceramics such as PMN-PZT, PMN-PZT-PT, PSN-PZN-PZT, PLN-PMN-PZT and the like have been widely studied, and these novel piezoelectric ceramics have a good development prospect.
The performance requirements of the piezoelectric ceramic materials of the piezoelectric ceramic devices with different requirements are different. Therefore, in order to produce materials with different properties and applications, the piezoelectric material needs to be modified. At present, two methods are mainly adopted at home and abroad: one is doping modification, namely doping certain impurity ions, and adjusting performance parameters of the material by carrying out a small amount of replacement on A-site or B-site ions so as to meet the requirements of piezoelectric components; the other is to improve the preparation process, such as determining the optimal calcination temperature, glue discharging system, polarization condition, etc., so that certain properties of the piezoelectric ceramic are improved to meet the requirements of piezoelectric components.
The niobium-antimony-lead zirconate titanate piezoelectric ceramic is a ceramic material with excellent piezoelectric performance, has higher piezoelectric coefficient and electromechanical coupling coefficient, has good frequency stability and time stability, and is widely applied to the fields of filters, vibrator underwater acoustic transducers, high-power drivers, automatic vehicle number reading devices, filter vibrators, high-temperature detection and high-temperature flaw detection and thickness measurement and the like. However, the piezoelectric ceramics of niobium-antimony-lead zirconate titanate obtained by the traditional polarization means still have lower piezoelectric coefficient and electromechanical coupling coefficient and poor temperature stability.
Disclosure of Invention
Aiming at the problems, the invention aims to provide high-temperature polarization-obtained high-voltage electrical performance niobium-antimony-lead zirconate titanate piezoelectric ceramic and a preparation process thereof, thereby overcoming the defects of low piezoelectric coefficient and electromechanical coupling coefficient and poor temperature stability of the traditional polarization-obtained niobium-antimony-lead zirconate titanate piezoelectric ceramic and effectively improving the comprehensive electrical performance of the niobium-antimony-lead zirconate titanate (PSN-PZT) piezoelectric ceramic.
In particular, on the one hand, the invention provides zinc-doped niobium-antimony-lead zirconate titanate piezoelectric ceramics, which comprises the following raw material components in percentage by mole: by Pb (Sb) 1/2 Nb 1/2 ) a Zr b Ti c O 3 On the basis, x mol% ZnO is added, wherein a=0.02 to 0.06, b=0.47 to 0.53, c=0.47 to 0.53 and a+b+c=1, x=0.2 to 0.8.
On the other hand, the invention also provides a preparation method of the zinc dioxide doped lead niobate-stibium zirconate titanate piezoelectric ceramic, which comprises the following steps: (1) batching; (2) synthesis; (3) fine grinding; (4) granulating; (5) molding; (6) plastic discharge; (7) sintering; (8) electrode coating; (9) high temperature polarization.
The invention selects the niobium-antimony-lead zirconate titanate piezoelectric ceramics as the object for research, and carries out high-temperature polarization process modification on the system to obtain the ideal piezoelectric ceramic material. High temperature polarization refers to heating a piezoelectric ceramic sample to above the curie temperature and applying a stable electric field during the polarization process, and then gradually cooling the piezoelectric ceramic sample to room temperature while maintaining the polarization electric field. In the process that the piezoelectric ceramic sample is gradually cooled to room temperature from the temperature above the Curie temperature, the electric field induces the ferroelectric domains to regrow and orient, so that the degree of orientation of the ferroelectric domains is improved, and the piezoelectric coefficient and the electromechanical coupling coefficient of the piezoelectric ceramic sample are improved. Meanwhile, the high-temperature polarization can also lead the defect dipoles in the piezoelectric ceramic sample to be distributed along the polarization electric field direction, so that the pinning effect of the defect dipoles on domain walls is enhanced, the domain walls are not easy to move under the outgoing effect, and the temperature stability of the piezoelectric ceramic sample is improved.
Preferably, the method comprises the steps of,the ingredients include: by Pb (Sb) 1/2 Nb 1/2 ) a Zr b Ti c O 3 Based on the addition of x mol% of ZnO, wherein a=0.02 to 0.06, b=0.47 to 0.53, c=0.47 to 0.53 and a+b+c=1, x=0.2 to 0.8, raw material Pb is weighed out 3 O 4 、Sb 2 O 3 、Nb 2 O 5 、ZrO 2 、TiO 2 Mixing with ZnO uniformly; ball milling is carried out on the evenly mixed raw materials, the ball milling medium is zirconium balls and water, and the raw materials are: ball: the mass ratio of water is 1:3:0.8, ball milling time is 4-6 h, and rotating speed is 260-380 r/min; drying the ball-milled mixed raw materials; and then, putting the dried mixed raw materials into a mortar for grinding, and sieving the ground mixed raw materials to obtain a sieve for standby.
Preferably, the synthesizing comprises: putting the undersize mixed raw materials obtained in the step (1) into a crucible, pressing into blocks, heating to 800-900 ℃ in a muffle furnace at a speed of 2-3 ℃/min, preserving heat and synthesizing for 2-4 h, and naturally cooling to room temperature along with the furnace and discharging to form powder.
Preferably, the fine grinding comprises: grinding the powder synthesized in the step (2), and then performing ball milling, wherein the ball milling medium comprises zirconium balls and water, and the following materials: ball: the weight ratio of water is 1:4:1 ball milling for 4-6 h at the rotating speed of 260-380 r/min, and drying the mixed powder after ball milling.
Preferably, the granulating comprises: grinding the powder material dried in the step (3) in a mortar, sieving, adding a polyvinyl alcohol solution with the mass concentration of 7% into the screen blanking, wherein the dosage of the polyvinyl alcohol solution relative to the screen blanking is 0.06-0.08 mL/g, fully and uniformly stirring, sieving, pressing the powder material into blocks, and aging for 24-48 hours.
Preferably, the forming includes: grinding the raw materials granulated in the step (4), sieving, and pressing the powder under the sieve into a disc-shaped blank.
Preferably, the plastic discharging includes: and (3) placing the blank obtained in the step (5) into a muffle furnace, heating to 650-750 ℃ at a speed of 2-3 ℃/min, preserving heat for 2-3 hours, and discharging organic matters.
Preferably, the sintering comprises: placing the blank subjected to plastic discharge in the step (6) into a crucible, sealing, using niobium-antimony-lead zirconate titanate ceramic powder as a burying material for burying and burning, keeping the temperature for 2-4 h at the temperature of 1220-1280 ℃ at the heating rate of 2-3 ℃/min, and naturally cooling to the room temperature along with a furnace.
Preferably, the cape electrode comprises: polishing the ceramic sheet sintered in the step (7) to a thickness of 1-2 mm, coating silver paste on the upper and lower surfaces of the ceramic sheet by adopting a screen printing process, placing the ceramic sheet in a muffle furnace, heating to 750-800 ℃ at a speed of 2-3 ℃/min, preserving heat for 10-20 min, and naturally cooling to room temperature.
Preferably, the high temperature polarization includes: the ceramic piece coated with the silver electrode in the step (8) is connected into a high-temperature polarization clamp, the clamp is placed into a muffle furnace to be heated to a polarization temperature, then voltage is regulated by a voltage stabilizing source to enable the polarization electric field to be 100-1000V/mm, then the voltage is kept unchanged, the ceramic piece is naturally cooled to room temperature, and then the voltage is removed, so that the niobium-antimony-lead zirconate titanate piezoelectric ceramic is prepared; wherein the polarization temperature is higher than the Curie temperature of the ceramic plate coated with the silver electrode, and the polarization temperature is preferably 350-500 ℃, and most preferably 400 ℃.
Advantageous effects
The invention provides a process method capable of improving the electrical property and the temperature stability of lead niobium-antimony-zirconate titanate (PSN-PZT) piezoelectric ceramics at the same time, and obtains the lead niobium-antimony-zirconate titanate (PSN-PZT) piezoelectric ceramic material with excellent electrical property and good temperature stability.
Drawings
FIG. 1 is a schematic diagram of a high temperature polarization apparatus used in the present invention;
FIG. 2 shows the piezoelectric constant d of PSN-PZT piezoelectric ceramic applied with polarized electric field of 50-1000V/mm in the process of gradually decreasing from 400℃to room temperature 33 Coefficient of electromechanical coupling k p And relative dielectric constant epsilon r Schematic representation of the effect;
FIG. 3 shows the piezoelectric constant d of a PSN-PZT piezoelectric ceramic sample polarized by an electric field of 500V/mm applied during gradual decrease from 400℃to room temperature and polarized in a conventional manner 33 A temperature stability comparison chart;
FIG. 4 shows the process of heating at 400℃in one stepApplying 500V/mm electric field polarization and PSN-PZT piezoelectric ceramic sample polarized in traditional mode during gradually cooling to room temperature r Temperature stability comparison graph.
Detailed Description
The invention will be further illustrated with reference to specific examples, it being understood that the scope of the invention is not limited to the description.
The invention provides high-temperature polarization-obtained high-voltage electrical performance niobium-antimony-lead zirconate titanate piezoelectric ceramic and a preparation process thereof, which overcome the defects of low piezoelectric coefficient and electromechanical coupling coefficient and poor temperature stability of the traditional polarization-obtained niobium-antimony-lead zirconate titanate piezoelectric ceramic, and effectively improve the comprehensive electrical performance of the niobium-antimony-lead zirconate titanate (PSN-PZT) piezoelectric ceramic.
The invention adopts the commercial chemical pure (purity is more than or equal to 99%) raw material Pb 3 O 4 、Sb 2 O 3 、Nb 2 O 5 、ZrO 2 、TiO 2 And ZnO, preparing zinc dioxide doped niobium-antimony-lead zirconate titanate piezoelectric ceramic, wherein the raw material components and the mol percentage content are as follows: by Pb (Sb) 1/2 Nb 1/2 ) a Zr b Ti c O 3 On the basis, x mol% ZnO is added, wherein a=0.02 to 0.06, b=0.47 to 0.53, c=0.47 to 0.53 and a+b+c=1, x=0.2 to 0.8. In some embodiments, the specific preparation method of the piezoelectric ceramic may include the following steps: compounding, synthesizing, fine grinding, granulating, forming, plastic discharging, sintering, electrode coating, high-temperature polarization and the like.
(1) And (5) batching. By Pb (Sb) 1/2 Nb 1/2 ) a Zr b Ti c O 3 On the basis, x mol% ZnO is added, wherein a=0.02 to 0.06, b=0.47 to 0.53, c=0.47 to 0.53 and a+b+c=1, x=0.2 to 0.8. Weighing raw material Pb according to the above formula 3 O 4 、Sb 2 O 3 、Nb 2 O 5 、ZrO 2 、TiO 2 And ZnO, mixing uniformly, and filling the uniformly mixed raw materials into a nylon tank for ball milling. In some embodiments, the ball milling media may be zirconium balls and waterAnd (2) material: ball: the weight ratio of water may be 1:3:0.8, the ball milling time can be 4-6 h, and the rotating speed can be 260-380 r/min. And (3) placing the ball-milled mixed raw materials into an oven, drying at 120 ℃, then placing the dried mixed raw materials into a mortar, grinding, further mixing and refining powder, and sieving the ground mixed raw materials with a 40-mesh sieve to obtain a sieve blanking for standby.
(2) And (5) synthesizing. Putting the undersize mixed raw material obtained in the step (1) into a crucible, pressing into a cylindrical block with the bottom surface diameter of about 60mm and the height of about 20-30 mm, capping and sealing, heating to 800-900 ℃ in a muffle furnace at the speed of 2-3 ℃/min, preserving heat and synthesizing for 2-4 h, and naturally cooling to room temperature along with the furnace and discharging to form powder.
(3) And (5) fine grinding. Grinding the powder synthesized in the step (2), and then filling the ground powder into a nylon tank for ball milling, wherein the ball milling medium is zirconium balls and water, and the following materials are prepared: ball: the weight ratio of water is 1:4:1 ball milling for 4-6 h at the rotating speed of 260-380 r/min, and placing the mixed powder in an oven for drying at 120 ℃. After fine grinding, powder D80 (80% of the powder particle size) is smaller than 1 μm, providing finer powder for the subsequent granulation process.
(4) Granulating. Grinding the powder dried in the step (3) in a mortar, sieving with a 60-mesh sieve to obtain a sieve blanking, adding a PVA (polyvinyl alcohol) solution with the mass concentration of 7% into the sieve blanking, wherein the PVA solution is used for 0.06-0.08 mL/g relative to the sieve blanking, fully and uniformly stirring, sieving, pressing the powder into blocks under the pressure of 600Mpa, and aging for 24-48 hours.
(5) And (5) molding. Grinding the raw materials after granulation in the step (4), sieving with a 40-mesh sieve, putting undersize powder into a stainless steel die with the diameter of 13mm, and pressing under 400Mpa pressure to form a disc-shaped blank with the diameter of 13 mm.
(6) And (5) plastic discharge. And (3) placing the blank obtained in the step (5) into a muffle furnace, heating to 650-750 ℃ at a speed of 2-3 ℃/min, preserving heat for 2-3 hours, and discharging organic matters.
(7) Sintering. Placing the blank subjected to plastic removal in the step (6) into a crucible, sealing, burying and burning by taking PSN-PZT powder as a burying material, preserving heat for 2-4 h at the temperature rising rate of 2-3 ℃/min and the temperature of 1220-1280 ℃, and naturally cooling to the room temperature along with a furnace.
(8) And (5) coating an electrode. Polishing the ceramic sheet sintered in the step (7) to a thickness of 1-2 mm, coating silver paste on the upper and lower surfaces of the ceramic sheet by adopting a screen printing process, placing the ceramic sheet in a muffle furnace, heating to 750-800 ℃ at a speed of 2-3 ℃/min, preserving heat for 10-20 min, and naturally cooling to room temperature.
(9) And (5) high-temperature polarization. The ceramic piece coated with the silver electrode in the step (8) is connected into a high-temperature polarization clamp according to the method shown in the figure 1, the clamp is placed into a muffle furnace to be heated to the polarization temperature, then the voltage is regulated by a voltage stabilizing source to enable the polarization electric field to be 100-1000V/mm, then the voltage is kept unchanged, the voltage is removed after the ceramic piece is naturally cooled to the room temperature, and the niobium-antimony-lead zirconate titanate piezoelectric ceramic is prepared; wherein the polarization temperature is higher than the Curie temperature of the ceramic plate coated with the silver electrode, and the polarization temperature is preferably 350-500 ℃, and most preferably 400 ℃.
And performing performance test on the prepared PSN-PZT piezoelectric ceramic. The piezoelectric ceramic sample is set to a required test temperature by using a memmer high-temperature oven, is kept for 30mins, and is externally connected with an E4990A impedance analyzer to measure required electrical performance parameters. Wherein the relative dielectric constant epsilon of the piezoelectric ceramic r (dimensionless) is calculated according to the following formula:
wherein C is the capacitance (F) of the sample, d is the thickness (m) of the sample, ε 0 Is vacuum dielectric constant (8.85×10) -12 F/m), S is the electrode area (m) of the sample 2 )。
Radial electromechanical coupling coefficient k of sample p According to the IEEE standard measurement, a table look-up method may be adopted or calculated by the following formula:
wherein k is p For the radial electromechanical coupling coefficient, f r 、f a The radial resonance frequency and the antiresonance frequency of the piezoelectric vibrator are respectively.
The invention adopts a ZJ-3A quasi-static tester of the national academy of sciences of China to measure the piezoelectric constant d according to the national standard GB11309-89 33 The unit is pC/N.
The preparation process and the related measurement parameters of the specific embodiments of the present invention are shown in the following table 1:
FIG. 2 shows the piezoelectric constant d of PSN-PZT piezoelectric ceramic applied with polarized electric field of 50-1000V/mm in the process of gradually decreasing from 400℃to room temperature 33 Coefficient of electromechanical coupling k p And relative dielectric constant epsilon r Schematic representation of the effect. As can be seen from FIG. 2, the PSN-PZT piezoelectric ceramic is polarized at high temperature under a polarization electric field higher than 100V/mm, the piezoelectric performance and the dielectric performance of the PSN-PZT piezoelectric ceramic are obviously improved compared with the traditional polarization mode, and the PSN-PZT piezoelectric ceramic is basically unchanged along with the improvement of the polarization electric field. The optimum performance parameter is obtained when the polarization electric field is 400V/mm and is d 33 ＝562pC/N，k p ＝0.671，ε r Material curie temperature t=2599 c Compared with the conventional polarization mode d =350℃ 33 Lifting to 16.6%, k p Raise the relative dielectric constant epsilon by 3.1 percent r The lifting rate is 11.8 percent.
FIG. 3 shows the piezoelectric constant d of a PSN-PZT piezoelectric ceramic sample polarized by an electric field of 500V/mm applied during gradual decrease from 400℃to room temperature and polarized in a conventional manner 33 A temperature stability comparison chart; FIG. 4 shows the relative permittivity ε of a PSN-PZT piezoelectric ceramic sample polarized by applying an electric field of 500V/mm during a gradual decrease from 400℃to room temperature r Temperature stability comparison graph. As can be seen from FIGS. 3 and 4, the PSN-PZT piezoelectric was superior to the conventional one in that a 3kV/mm electric field was applied in silicone oil at 180 deg.CThe PSN-PZT piezoelectric ceramics with high-temperature polarization have higher temperature stability.
The PSN-PZT piezoelectric ceramic prepared by the method can be used for preparing devices with high requirements on the performance of the piezoelectric ceramic, such as a water acoustic sensor, a high-temperature transducer and the like.
Claims (11)
1. The zinc-doped niobium-antimony-lead zirconate titanate piezoelectric ceramic is characterized by comprising the following raw material components in percentage by mole: by Pb (Sb) 1/2 Nb 1/2 ) a Zr b Ti c O 3 On the basis, x mol% ZnO is added, wherein a=0.02 to 0.06, b=0.47 to 0.53, c=0.47 to 0.53 and a+b+c=1, x=0.2 to 0.8.
2. A method for producing zinc dioxide-doped lead niobate-stibium zirconate titanate piezoelectric ceramic according to claim 1, comprising the steps of: (1) batching; (2) synthesis; (3) fine grinding; (4) granulating; (5) molding; (6) plastic discharge; (7) sintering; (8) electrode coating; (9) high temperature polarization.
3. The method of preparing according to claim 2, wherein the ingredients comprise: by Pb (Sb) 1/2 Nb 1/2 ) a Zr b Ti c O 3 Based on the addition of x mol% of ZnO, wherein a=0.02 to 0.06, b=0.47 to 0.53, c=0.47 to 0.53 and a+b+c=1, x=0.2 to 0.8, raw material Pb is weighed out 3 O 4 、Sb 2 O 3 、Nb 2 O 5 、ZrO 2 、TiO 2 Mixing with ZnO uniformly; ball milling is carried out on the evenly mixed raw materials, the ball milling medium is zirconium balls and water, and the raw materials are: ball: the mass ratio of water is 1:3:0.8, ball milling time is 4-6 h, and rotating speed is 260-380 r/min; drying the ball-milled mixed raw materials; and then, putting the dried mixed raw materials into a mortar for grinding, and sieving the ground mixed raw materials to obtain a sieve for standby.
4. A method of preparation according to claim 2 or 3, wherein the synthesis comprises: putting the undersize mixed raw materials obtained in the step (1) into a crucible, pressing into blocks, heating to 800-900 ℃ in a muffle furnace at a speed of 2-3 ℃/min, preserving heat and synthesizing for 2-4 h, and naturally cooling to room temperature along with the furnace and discharging to form powder.
5. The production method according to any one of claims 2 to 4, wherein the fine grinding comprises: grinding the powder synthesized in the step (2), and then performing ball milling, wherein the ball milling medium comprises zirconium balls and water, and the following materials: ball: the weight ratio of water is 1:4:1 ball milling for 4-6 h at the rotating speed of 260-380 r/min, and drying the mixed powder after ball milling.
6. The method of any one of claims 2 to 5, wherein the granulating comprises: grinding the powder dried in the step (3) in a mortar, sieving, adding a polyvinyl alcohol solution with the mass concentration of 7% into the screen blanking, wherein the dosage of the polyvinyl alcohol solution relative to the screen blanking is 0.06-0.08 mL/g, fully and uniformly stirring, sieving, pressing the powder into blocks, and aging for 24-48 hours.
7. The production method according to any one of claims 2 to 6, characterized in that the molding comprises: grinding the raw materials granulated in the step (4), sieving, and pressing the powder under the sieve into a disc-shaped blank.
8. The method of any one of claims 2 to 7, wherein the plastic displacement comprises: and (3) placing the blank obtained in the step (5) into a muffle furnace, heating to 650-750 ℃ at a speed of 2-3 ℃/min, preserving heat for 2-3 hours, and discharging organic matters.
9. The method of any one of claims 2 to 8, wherein the sintering comprises: placing the blank subjected to plastic discharge in the step (6) into a crucible, sealing, using niobium-antimony-lead zirconate titanate ceramic powder as a burying material for burying and burning, keeping the temperature for 2-4 h at the temperature of 1220-1280 ℃ at the heating rate of 2-3 ℃/min, and naturally cooling to the room temperature along with a furnace.
10. The method of any one of claims 2 to 9, wherein the cape electrode comprises: polishing the ceramic sheet sintered in the step (7) to a thickness of 1-2 mm, coating silver paste on the upper and lower surfaces of the ceramic sheet by adopting a screen printing process, placing the ceramic sheet in a muffle furnace, heating to 750-800 ℃ at a speed of 2-3 ℃/min, preserving heat for 10-20 min, and naturally cooling to room temperature.
11. The method of any one of claims 2 to 10, wherein the high temperature polarization comprises: the ceramic piece coated with the silver electrode in the step (8) is connected into a high-temperature polarization clamp, the clamp is placed into a muffle furnace to be heated to a polarization temperature, then voltage is regulated by a voltage stabilizing source to enable the polarization electric field to be 100-1000V/mm, then the voltage is kept unchanged, the ceramic piece is naturally cooled to room temperature, and then the voltage is removed, so that the niobium-antimony-lead zirconate titanate piezoelectric ceramic is prepared; wherein the polarization temperature is higher than the Curie temperature of the ceramic plate coated with the silver electrode, and the polarization temperature is preferably 350-500 ℃, and most preferably 400 ℃.
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| JPH07202291A (en) * | 1993-12-29 | 1995-08-04 | Tdk Corp | Manufacture of piezoelectric ceramic |
| JP2016199433A (en) * | 2015-04-10 | 2016-12-01 | Tdk株式会社 | Piezoelectric ceramic and piezoelectric element |
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| JPH07202291A (en) * | 1993-12-29 | 1995-08-04 | Tdk Corp | Manufacture of piezoelectric ceramic |
| JP2016199433A (en) * | 2015-04-10 | 2016-12-01 | Tdk株式会社 | Piezoelectric ceramic and piezoelectric element |
| CN109503158A (en) * | 2018-12-17 | 2019-03-22 | 贵州振华红云电子有限公司 | A kind of piezoceramic material and preparation method thereof of resistance to temperature shock |
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