CN115215667B - Lead-based piezoelectric ceramic and preparation method thereof - Google Patents

Lead-based piezoelectric ceramic and preparation method thereof Download PDF

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CN115215667B
CN115215667B CN202210898075.0A CN202210898075A CN115215667B CN 115215667 B CN115215667 B CN 115215667B CN 202210898075 A CN202210898075 A CN 202210898075A CN 115215667 B CN115215667 B CN 115215667B
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sintering
lead
ceramic
piezoelectric ceramic
based piezoelectric
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CN115215667A (en
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毕鲁南
李伶
王营营
赵杰
王晓东
王伟伟
隋松林
徐先豹
王飞
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Shandong Industrial Ceramics Research and Design Institute Co Ltd
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Shandong Industrial Ceramics Research and Design Institute Co Ltd
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Abstract

The invention discloses a lead-based piezoelectric ceramic and a preparation method thereof, comprising the following steps: preparing ceramic slurry, and performing photo-curing forming treatment on the ceramic slurry to obtain a ceramic blank; sintering the ceramic blank to obtain lead-based piezoelectric ceramic; and the ceramic blank is subjected to primary drying, extraction and secondary drying in sequence before the sintering treatment, wherein the sintering treatment comprises degreasing sintering and secondary sintering, and the degreasing sintering adopts a partial pressure sintering mode, and the pressure is between-0.3 MPa and 0.6MPa.

Description

Lead-based piezoelectric ceramic and preparation method thereof
Technical Field
The invention belongs to the technical field of piezoelectric ceramics, and particularly relates to lead-based piezoelectric ceramics and a preparation method thereof.
Background
The piezoelectric composite material has unique performance and can be applied to the fields of ultrasonic detection, ultrasonic diagnosis and the like. The piezoelectric composite material is usually composed of a special-shaped ceramic matrix and an organic filler, and the existing preparation process of the piezoelectric ceramic matrix is mostly a mechanical cutting method or an injection molding method, but the piezoelectric ceramic prepared by the mechanical cutting method is too single in shape, and the piezoelectric ceramic prepared by the injection molding method is low in density, so that the electrical property of the piezoelectric ceramic is seriously influenced, and the practical application of the piezoelectric ceramic is hindered.
Disclosure of Invention
In view of the above problems, in a first aspect, the present invention provides a method for preparing a lead-based piezoelectric ceramic, comprising the steps of:
preparing ceramic slurry, and performing photo-curing forming treatment on the ceramic slurry to obtain a ceramic blank;
sintering the ceramic blank to obtain lead-based piezoelectric ceramic;
and the ceramic blank is subjected to primary drying, extraction and secondary drying in sequence before the sintering treatment, wherein the sintering treatment comprises degreasing sintering and secondary sintering, and the degreasing sintering adopts a partial pressure sintering mode, and the pressure is between-0.3 MPa and 0.6MPa.
Compared with the prior art, the invention has the beneficial effects that: the photocuring is adopted to form the ceramic blank, so that the special-shaped piezoelectric ceramic is prepared, and the shape of the ceramic is more diversified;
the drying treatment of the ceramic blank comprises drying, extraction and secondary drying, which is favorable for removing organic matters in the blank, keeping the shape of the blank and preventing the blank from cracking;
the lead-based ceramic green body has different liquid phase proportion and liquid phase viscosity, so that the corresponding optimal sintering air pressure is different, and the degreasing sintering stage adopts a partial pressure sintering mode, thereby being beneficial to accelerating mass transfer of liquid phase substances in the green body, effectively discharging internal defects and improving the density of the green body; meanwhile, the pressure born by the ceramic blank body under different air pressures is different, so that the problem of deformation caused by larger force can be avoided, and the fine structure of the photo-curing molding lead-based ceramic is favorably maintained.
Preferably, the partial pressure sintering comprises four stages, the highest sintering temperature T of the partial pressure sintering max Is 1400-1600 ℃,
wherein the first stage is carried out under the conditions of room temperature to 600 ℃ and pressure of 0.4 to 0.6MPa, the temperature rising rate is 0.5 to 1.5 ℃/min, and the heat preservation is carried out for 1 to 3 hours;
the second stage is carried out under the conditions of 600-1000 ℃ and standard atmospheric pressure, the temperature rising rate is 0.3-1 ℃/min, and the temperature is kept for 3-5h;
the third stage is under the temperature of 1000 ℃ to (T) max -100 ℃ and under the conditions of the pressure of-0.1 MPa to-0.3 MPa, the temperature rising rate of 0.3-1 ℃/min and the heat preservation of 3-5h;
the fourth stage is at (T max -100℃)～T max The process is carried out under the conditions of the pressure of minus 0.01MPa to minus 0.03MPa, the heating rate of 0.2 to 0.5 ℃/min and the heat preservation of 5 to 7 hours.
The beneficial effects of this preferred scheme are: because the liquid phase proportion of the lead-based ceramic green bodies in different sintering temperature sections is different, the ceramic green bodies are sintered by adopting sectional pressure, negative pressure is applied to the ceramic green bodies, and when high-pressure bubbles in the green bodies are in a low-pressure system, the surface tension of the high-pressure bubbles is insufficient to maintain the stability of the system due to pressure balance, so that the defects in the green bodies can be discharged by utilizing pressure difference under the negative pressure environment.
Preferably, the primary drying includes: drying at 60-80deg.C for 20-28 hr;
the extraction process is carried out at the temperature of 80-100 ℃, and the extractant is polyethylene glycol or kerosene;
the secondary drying comprises the following steps: drying at 80-120deg.C for 20-28 hr.
The beneficial effects of this preferred scheme are: the low boiling point substances (water and auxiliary agents) in the blank body can be effectively removed by one-time drying, and partial solvent in the blank body can be discharged by utilizing the principle of different solubilities in extraction, so that the organic matters in the blank body can be removed, the shape of the blank body can be maintained, and the blank body is not cracked.
Preferably, the degreasing sintering stage is performed under an oxygen atmosphere.
The beneficial effects of this preferred scheme are: oxygen vacancies in the form of point defects exist in the ceramic blank, and the introduced oxygen is favorable for filling the oxygen vacancies, so that the density of the ceramic is further improved.
Preferably, the secondary sintering adopts a hot isostatic pressing sintering mode, the sintering temperature is 1200-1400 ℃, and the sintering time is 4-8 h.
The beneficial effects of this preferred scheme are: and the secondary sintering adopts hot isostatic pressing, which is beneficial to improving the density of the ceramic.
Preferably, the preparation method of the ceramic slurry comprises the following steps:
uniformly mixing a monomer, a photoinitiator and an auxiliary agent to obtain photosensitive resin;
uniformly mixing organic silicon resin, lead-based ceramic powder and absolute ethyl alcohol to obtain pretreated powder;
and uniformly mixing the pretreatment powder with photosensitive resin to obtain ceramic slurry.
The beneficial effects of this preferred scheme are: the organic silicon resin can be used for organizing the lead-based ceramic powder, the organic silicon resin and the lead-based ceramic powder are mixed, the lead-based ceramic powder is modified by the organic silicon resin, and the dispersibility of the lead-based ceramic powder in the photosensitive resin is improved by the principle of polarity compatibility.
Preferably, the monomer is an acrylic monomer, the photoinitiator is one or more of photoinitiator 819, photoinitiator 184 and photoinitiator TPO,
the weight of the monomer is 55-65 parts, the weight of the photoinitiator is 0.5-0.7 part, and the weight of the auxiliary agent is 24-28 parts.
The organic silicon resin is 1-5 parts by weight, the lead-based ceramic powder is 95-100 parts by weight, and the absolute ethyl alcohol is 95-100 parts by weight.
Preferably, the auxiliary agent comprises a first dispersing agent, a second dispersing agent and an anti-settling agent, wherein the first dispersing agent comprises one or more of BYK110, BYK103, KOS163, triton X-100 and triton X-114; the second dispersant comprises Dachuan H059 and BYK190, and the anti-settling agent comprises an anti-settling agent BYK420 and an anti-settling agent DH690.
The beneficial effects of this preferred scheme are: the second dispersant can disperse ceramic powder, and in the polar matching medium, solvated chains extend into the dispersing medium, so that polymers on adjacent particles repel each other due to volume effect, and the suspension stability of the system is effectively maintained. The anti-settling agent has an electrostatic stabilizing effect and can prevent the dispersed powder from settling.
In a second aspect, the invention also provides a lead-based piezoelectric ceramic, which is prepared by the preparation method of any one of the lead-based piezoelectric ceramics.
Compared with the prior art, the invention has the beneficial effects that: by the method for preparing the lead-based piezoelectric ceramic, the special-shaped ceramic is prepared, and internal defects of the green body can be effectively discharged in a partial pressure sintering mode, so that the density of the green body is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below in connection with the embodiments of the present invention.
Example 1
The embodiment provides a preparation method of lead-based piezoelectric ceramic, which comprises the following steps:
step 1: weighing 55-65 parts of monomer, wherein the monomer is acrylic ester, and specifically comprises the following 3 types: one or more of 4-tert-butylcyclohexyl acrylate (TBCHA), cyclohexyl methacrylate (CHMA), polyhydroxyethyl methyl acrylate (PHEMA), one or more of 1, 6-hexanediol dimethacrylate (HDDMA), hexanediol diacrylate (HDDA), tetraethylene glycol dimethacrylate (TEGDMA), polyethylene glycol 400 diacrylate (PEG 400 DA), one or more of pentaerythritol triacrylate (PETA), ethoxylated pentaerythritol tetraacrylate (PPTTA), trimethylolpropane triacrylate (TMPTA). According to the following steps of 1:1:1, weighing 3 types of acrylic ester, and mixing by using an ultrasonic vibration machine.
Step 2: weighing 10-14 parts of a first dispersing agent and 10-14 parts of an anti-settling agent, adding into the solution mixed in the step 1, and mixing by using an ultrasonic oscillator. Preferably, the first dispersant comprises one or more of BYK110, BYK103, KOS163, triton X-100 and triton X-114, and the anti-settling agent comprises BYK420 and DH690.
Step 3: weighing 0.5-0.7 part of photoinitiator, adding the photoinitiator into the solution mixed in the step 2, and mixing by using an ultrasonic oscillator. Preferably, the photoinitiator comprises one or more of 819, 184 and TPO.
Step 4: weighing 1-3 parts of a second dispersing agent, adding the second dispersing agent into the solution mixed in the step 3, and mixing by using an ultrasonic vibration machine to obtain the photosensitive resin. Preferably, the second dispersant includes Dachuan H059 and BYK190.
Step 5: 1-5 parts of organic silicon resin, 95-100 parts of lead-based ceramic powder and 95-100 parts of absolute ethyl alcohol are weighed, ball milling and mixing treatment are carried out by using a ball mill, and pretreated powder is obtained, so that the organic silicon resin is attached to the surface of the ceramic powder to play a role in modification.
Step 6: weighing 55-65 parts of the pretreated powder obtained in the step 5, adding the pretreated powder into the photosensitive resin obtained in the step 4 in batches, and performing dispersion treatment by using a high-energy ball mill to obtain ceramic slurry. In the embodiment, the ball milling speed is preferably 90-110r/min, and the time is preferably 10-14h.
Step 7: and (3) performing photocuring forming on the ceramic slurry by using a photocuring 3D printer to obtain a ceramic blank. The printer preferably has an oxygen barrier film.
Step 8: and (3) carrying out primary drying treatment on the ceramic blank by using a vacuum drying oven, wherein the drying temperature is 60-80 ℃ and the drying time is 20-28h. Can effectively remove partial low boiling point substances such as water and auxiliary agents in the blank body.
Step 9: and extracting the ceramic body after primary drying by using an extractant, and further discharging water. In this embodiment, preferably, the extraction temperature is 80-100deg.C, and the extractant is polyethylene glycol or kerosene. The solvent in the blank body can be discharged by utilizing the principle of different solubilities, which is favorable for organic matters in the blank body, and the shape of the blank body is kept so as not to crack.
Step 10: and (5) drying the extracted green body for the second time by using a vacuum drying box. In this embodiment, the secondary drying temperature is preferably 80-120 ℃ and the time is 20-28h.
Step 11: the ceramic body after the secondary drying is degreased and sintered by using a tube furnace, and in this embodiment, the degreasing and sintering stage is preferably performed under an oxygen atmosphere. The degreasing sintering treatment adopts a partial pressure sintering mode, the partial pressure sintering comprises four stages, and the maximum sintering temperature T of the partial pressure sintering max Is 1400-1600 ℃,
wherein the first stage is carried out under the conditions of room temperature to 600 ℃ and pressure of 0.4 to 0.6MPa, the temperature rising rate is 0.5 to 1.5 ℃/min, and the heat preservation is carried out for 1 to 3 hours;
the second stage is carried out under the conditions of 600-1000 ℃ and standard atmospheric pressure, the temperature rising rate is 0.5-1.5 ℃/min, and the temperature is kept for 1-3h;
the third stage is under the temperature of 1000 ℃ to (T) max -100 ℃ and under the conditions of the pressure of-0.1 MPa to-0.3 MPa, the temperature rising rate of 0.3-1 ℃/min and the heat preservation of 3-5h;
the fourth stage is at (T max -100℃)～T max The process is carried out under the conditions of the pressure of minus 0.01MPa to minus 0.03MPa, the heating rate of 0.2 to 0.5 ℃/min and the heat preservation of 5 to 7 hours.
Step 12: and (3) performing secondary sintering on the degreased and sintered ceramic blank by using a hot isostatic pressing sintering furnace, wherein the secondary sintering temperature is 1200-1400 ℃ to obtain a lead-based piezoelectric ceramic product.
Example 2
Step 1: 55 parts of monomers, which are acrylic esters, are weighed, preferably according to 1:1:1 4-t-butylcyclohexyl acrylate (TBCHA), 1,6 hexanediol dimethacrylate (HDDMA), pentaerythritol triacrylate (PETA) were weighed and mixed using an ultrasonic shaker.
Step 2: weighing 10 parts of a first dispersing agent and 14 parts of an anti-settling agent, adding the first dispersing agent and the anti-settling agent into the solution mixed in the step 1, and mixing by using an ultrasonic vibration machine. Preferably, the first dispersant comprises triton X-100 and triton X-114, and the anti-settling agent comprises BYK420.
Step 3: and (2) weighing 0.5 part of photoinitiator, adding the photoinitiator into the solution mixed in the step (2), and mixing by using an ultrasonic oscillator. Preferably, in this embodiment, the photoinitiator is 819.
Step 4: and (3) weighing 1 part of the second dispersing agent, adding the second dispersing agent into the solution mixed in the step (3), and mixing by using an ultrasonic vibration machine to obtain the photosensitive resin. Preferably, the second dispersant includes dahurian H059.
Step 5: 1 part of organic silicon resin, 95 parts of lead-based ceramic powder and 95 parts of absolute ethyl alcohol are weighed, ball milling and mixing treatment are carried out by using a ball mill, so as to obtain pretreated powder, and the organic silicon resin is attached to the surface of the ceramic powder to play a role in modification.
Step 6: and (3) weighing 55 parts of the pretreated powder obtained in the step (5), adding the pretreated powder into the photosensitive resin obtained in the step (4) in batches, and performing dispersion treatment by using a high-energy ball mill to obtain ceramic slurry. In this example, the ball milling speed is preferably 90r/min and the time is 14h.
Step 7: and (3) performing photocuring forming on the ceramic slurry by using a photocuring 3D printer to obtain a ceramic blank. The printer preferably has an oxygen barrier film.
Step 8: and (3) carrying out primary drying treatment on the ceramic blank by using a vacuum drying oven, wherein the drying temperature is 60 ℃ and the time is 28 hours. Can effectively remove partial low boiling point substances such as water and auxiliary agents in the blank body.
Step 9: and extracting the dried ceramic body by using an extractant, and further discharging water. In this embodiment, the extraction temperature is preferably 80 ℃, and the extractant is polyethylene glycol or kerosene. The solvent in the blank body can be discharged by utilizing the principle of different solubilities, which is favorable for organic matters in the blank body, and the shape of the blank body is kept so as not to crack.
Step 10: and (5) drying the extracted green body for the second time by using a vacuum drying box. In this embodiment, the secondary drying temperature is preferably 80 ℃ and the time is 28 hours.
Step 11: the ceramic body after the secondary drying is degreased and sintered by using a tube furnace, and in this embodiment, the degreasing and sintering stage is preferably performed under an oxygen atmosphere. The degreasing sintering treatment adopts a partial pressure sintering mode, the partial pressure sintering comprises four stages, and the maximum sintering temperature T of the partial pressure sintering max At a temperature of 1400 c, and in particular,
the first stage is carried out at room temperature to 600 ℃ and under the pressure of 0.6MPa, the heating rate is 0.5 ℃/min, and the temperature is kept for 3 hours;
the second stage is carried out under the conditions of 600-1000 ℃ and standard atmospheric pressure, the temperature rising rate is 0.5 ℃/min, and the heat preservation is carried out for 4 hours;
the third stage is carried out under the conditions of 1000-1300 ℃ and the pressure of minus 0.3MPa, the heating rate is 0.3 ℃/min, and the heat preservation is carried out for 5 hours;
the fourth stage is carried out under the conditions of 1300-1400 ℃ and the pressure of minus 0.03MPa, the heating rate is 0.2 ℃/min, and the heat preservation is carried out for 7 hours.
Step 12: and (3) performing secondary sintering on the degreased and sintered ceramic blank by using a hot isostatic pressing sintering furnace, wherein the secondary sintering temperature is 1250 ℃, and obtaining the lead-based piezoelectric ceramic product.
Example 3
Step 1: 60 parts of monomers, which are acrylic esters, are weighed, preferably according to 1:1:1, weighing cyclohexyl methacrylate (CHMA), polyhydroxyethyl methyl acrylate (PHEMA), hexanediol diacrylate (HDDA) and ethoxylated pentaerythritol tetraacrylate (PPTTA), and mixing by using an ultrasonic vibration machine.
Step 2: weighing 12 parts of a first dispersing agent and 12 parts of an anti-settling agent, adding the first dispersing agent and the anti-settling agent into the solution mixed in the step 1, and mixing by using an ultrasonic vibration machine. Preferably, in this embodiment, the first dispersant is BYK110, and the anti-settling agent includes DH690.
Step 3: and (2) weighing 0.6 part of photoinitiator, adding the photoinitiator into the solution mixed in the step (2), and mixing by using an ultrasonic oscillator. Preferably, the photoinitiator comprises 184 and TPO.
Step 4: and 2 parts of a second dispersing agent is weighed and added into the solution mixed in the step 3, and an ultrasonic vibration machine is used for mixing to obtain the photosensitive resin. Preferably, the second dispersant includes BYK190.
Step 5: 2 parts of organic silicon resin, 100 parts of lead-based ceramic powder and 100 parts of absolute ethyl alcohol are weighed, ball milling and mixing treatment are carried out by using a ball mill, so as to obtain pretreated powder, and the organic silicon resin is attached to the surface of the ceramic powder to play a role in modification.
Step 6: 60 parts of the pretreated powder obtained in the step 5 are weighed and added into the photosensitive resin obtained in the step 4 in batches, and a high-energy ball mill is used for carrying out dispersion treatment to obtain ceramic slurry. In the embodiment, the ball milling speed is preferably 100r/min, and the time is preferably 12h.
Step 7: and (3) performing photocuring forming on the ceramic slurry by using a photocuring 3D printer to obtain a ceramic blank. The printer preferably has an oxygen barrier film.
Step 8: and (3) carrying out primary drying treatment on the ceramic blank by using a vacuum drying oven, wherein the drying temperature is 70 ℃ and the time is 24 hours. Can effectively remove partial low boiling point substances such as water and auxiliary agents in the blank body.
Step 9: and extracting the dried ceramic body by using an extractant, and further discharging water. In this embodiment, preferably, the extraction temperature is 90 ℃, and the extractant is polyethylene glycol or kerosene. The solvent in the blank body can be discharged by utilizing the principle of different solubilities, which is favorable for organic matters in the blank body, and the shape of the blank body is kept so as not to crack.
Step 10: and (5) drying the extracted green body for the second time by using a vacuum drying box. In this embodiment, the secondary drying temperature is preferably 100 ℃ and the time is 24 hours.
Step 11: the ceramic body after the secondary drying is degreased and sintered by using a tube furnace, and in this embodiment, the degreasing and sintering stage is preferably performed under an oxygen atmosphere. The degreasing sintering treatment adopts a partial pressure sintering mode, the partial pressure sintering comprises four stages, and the maximum sintering temperature T of the partial pressure sintering max At a temperature of 1500 c, in particular,
the first stage is carried out at room temperature to 600 ℃ and under the pressure of 0.5MPa, the heating rate is 1 ℃/min, and the temperature is kept for 2 hours;
the second stage is carried out under the conditions of 600-1000 ℃ and standard atmospheric pressure, the heating rate is 1 ℃/min, and the temperature is kept for 2 hours;
the third stage is carried out under the conditions of 1000-1400 ℃ and the pressure of minus 0.2MPa, the heating rate is 0.5 ℃/min, and the temperature is kept for 4 hours;
the fourth stage is carried out under the conditions of 1400-1450 ℃ and pressure of-0.02 MPa, the heating rate is 0.25 ℃/min, and the temperature is kept for 6h.
Step 12: and (3) performing secondary sintering on the ceramic blank subjected to degreasing sintering by using a hot isostatic pressing sintering furnace, wherein the secondary sintering temperature is 1300 ℃, and obtaining the lead-based piezoelectric ceramic product.
Example 4
Step 1: 65 parts of a monomer, which is an acrylate, are weighed, and in this example, preferably, the monomer is prepared according to a ratio of 1:1:1, weighing and mixing polyhydroxyethyl methyl acrylate (PHEMA), tetraethyleneglycol dimethacrylate (TEGDMA) and trimethylolpropane triacrylate (TMPTA) by using an ultrasonic vibration machine.
Step 2: weighing 14 parts of a first dispersing agent and 10 parts of an anti-settling agent, adding the first dispersing agent and the anti-settling agent into the solution mixed in the step 1, and mixing by using an ultrasonic vibration machine. Preferably, the first dispersant comprises BYK103 and triton X-100, and the anti-settling agent comprises BYK420.
Step 3: and (2) weighing 0.7 part of photoinitiator, adding the photoinitiator into the solution mixed in the step (2), and mixing by using an ultrasonic oscillator. Preferably, in this embodiment, the photoinitiator is TPO.
Step 4: and 3 parts of a second dispersing agent is weighed and added into the solution mixed in the step 3, and an ultrasonic vibration machine is used for mixing to obtain the photosensitive resin. Preferably, the second dispersant includes Dachuan H059 and BYK190.
Step 5: 4 parts of organic silicon resin, 100 parts of lead-based ceramic powder and 100 parts of absolute ethyl alcohol are weighed, ball milling and mixing treatment are carried out by using a ball mill, so as to obtain pretreated powder, and the organic silicon resin is attached to the surface of the ceramic powder to play a role in modification.
Step 6: 65 parts of the pretreated powder obtained in the step 5 is weighed and added into the photosensitive resin obtained in the step 4 for 3 times, and a high-energy ball mill is used for carrying out dispersion treatment to obtain ceramic slurry. In this example, the ball milling speed is preferably 110r/min and the time is 10 hours.
Step 7: and (3) performing photocuring forming on the ceramic slurry by using a photocuring 3D printer to obtain a ceramic blank. The printer preferably has an oxygen barrier film.
Step 8: and (3) carrying out primary drying treatment on the ceramic blank by using a vacuum drying oven, wherein the drying temperature is 80 ℃ and the time is 20 hours. Can effectively remove partial low boiling point substances such as water and auxiliary agents in the blank body.
Step 9: and extracting the dried ceramic body by using an extractant, and further discharging water. In this embodiment, preferably, the extraction temperature is 100 ℃, and the extractant is polyethylene glycol or kerosene. The solvent in the blank body can be discharged by utilizing the principle of different solubilities, which is favorable for organic matters in the blank body, and the shape of the blank body is kept so as not to crack.
Step 10: and (5) drying the extracted green body for the second time by using a vacuum drying box. In this embodiment, the secondary drying temperature is preferably 120 ℃ and the time is 20 hours.
Step 11: the ceramic body after the secondary drying is degreased and sintered by using a tube furnace, and in this embodiment, the degreasing and sintering stage is preferably performed under an oxygen atmosphere. The degreasing sintering treatment adopts a partial pressure sintering mode, the partial pressure sintering comprises four stages, and the maximum sintering temperature T of the partial pressure sintering max At a temperature of 1600 c, and in particular,
the first stage is carried out at room temperature to 600 ℃ and under the pressure of 0.4MPa, the heating rate is 1.5 ℃/min, and the temperature is kept for 1.5h;
the second stage is carried out under the conditions of 600-1000 ℃ and standard atmospheric pressure, the temperature rising rate is 1.5 ℃/min, and the heat preservation is carried out for 1h;
the third stage is carried out under the conditions of 1000 ℃ to 1500 ℃ and the pressure of minus 0.1MPa, the heating rate is 1 ℃/min, and the heat preservation is carried out for 3 hours;
the fourth stage is carried out under the conditions of 1500-1600 ℃ and pressure of-0.01 MPa, the heating rate is 0.5 ℃/min, and the temperature is kept for 5h.
Step 12: and (3) performing secondary sintering on the degreased and sintered ceramic blank by using a hot isostatic pressing sintering furnace, wherein the secondary sintering temperature is 1350 ℃ to obtain a lead-based piezoelectric ceramic product.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention. Although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (8)

1. The preparation method of the lead-based piezoelectric ceramic is characterized by comprising the following steps of:
preparing ceramic slurry, and performing photo-curing forming treatment on the ceramic slurry to obtain a ceramic blank;
sintering the ceramic blank to obtain lead-based piezoelectric ceramic;
the method comprises the steps of sequentially carrying out primary drying, extraction and secondary drying on a ceramic blank before sintering, wherein the sintering comprises degreasing sintering and secondary sintering, and the degreasing sintering adopts a partial pressure sintering mode, and the pressure is-0.3 MPa to 0.6MPa;
the partial pressure sintering comprises four stages, and the maximum sintering temperature T of the partial pressure sintering max Is 1400-1600 ℃,
the first stage is carried out at room temperature to 600 ℃ and under the pressure of 0.4-0.6 MPa;
the second stage is carried out at 600-1000 ℃ under the condition that the pressure is standard atmospheric pressure;
the third stage is at 1000 ℃ to (T) max -100 ℃ and the pressure is-0.1 MPa to-0.3 MPa;
the fourth stage is at (T max -100℃）~T max The pressure is-0.01 MPa to-0.03 MPa.
2. The method for producing a lead-based piezoelectric ceramic according to claim 1, wherein the primary drying comprises: drying at 60-80deg.C for 20-28h;
the extraction process is carried out at the temperature of 80-100 ℃, and the extractant is polyethylene glycol or kerosene;
the secondary drying comprises the following steps: drying at 80-120deg.C for 20-28 hr.
3. The method for preparing a lead-based piezoelectric ceramic according to claim 1, wherein the degreasing and sintering stage is performed under an oxygen atmosphere.
4. The method for preparing lead-based piezoelectric ceramic according to claim 1, wherein the secondary sintering adopts a hot isostatic pressing sintering mode, and the sintering temperature is 1200-1400 ℃.
5. The method for producing a lead-based piezoelectric ceramic according to claim 1, wherein the method for producing a ceramic slurry comprises the steps of:
uniformly mixing a monomer, a photoinitiator and an auxiliary agent to obtain photosensitive resin;
uniformly mixing organic silicon resin, lead-based ceramic powder and absolute ethyl alcohol to obtain pretreated powder;
and uniformly mixing the pretreatment powder with photosensitive resin to obtain ceramic slurry.
6. The method of preparing a lead-based piezoelectric ceramic according to claim 5, wherein the monomer is an acrylic monomer, the photoinitiator comprises one or more of photoinitiator 819, photoinitiator 184, and photoinitiator TPO,
the weight of the monomer is 55-65 parts, the weight of the photoinitiator is 0.5-0.7 part, and the weight of the auxiliary agent is 24-28 parts.
7. The method for preparing lead-based piezoelectric ceramic according to claim 5, wherein the weight of the organic silicon resin is 1-5 parts, the weight of the lead-based ceramic powder is 95-100 parts, and the weight of the absolute ethyl alcohol is 95-100 parts.
8. A lead-based piezoelectric ceramic, characterized in that it is produced according to the production method of the lead-based piezoelectric ceramic according to any one of claims 1 to 7.
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