CN113956040A - Transparent photoelectric ceramic material with ultrahigh voltage coefficient and ultrahigh photoluminescence performance and preparation method thereof - Google Patents

Transparent photoelectric ceramic material with ultrahigh voltage coefficient and ultrahigh photoluminescence performance and preparation method thereof Download PDF

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CN113956040A
CN113956040A CN202010699470.7A CN202010699470A CN113956040A CN 113956040 A CN113956040 A CN 113956040A CN 202010699470 A CN202010699470 A CN 202010699470A CN 113956040 A CN113956040 A CN 113956040A
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ceramic material
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CN113956040B (en
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曾江涛
郑嘹赢
李国荣
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a transparent photoelectric ceramic material with ultrahigh voltage coefficient and ultrahigh photoluminescence performance and a preparation method thereof, wherein the transparent photoelectric ceramic material has the following general formula: pb1‑ yPry[(Mg1/3Nb2/3)1‑xTix]1‑y/4O3Wherein x is more than or equal to 0.28 and less than or equal to 0.35, and y is more than or equal to 0.005 and less than or equal to 0.04.

Description

Transparent photoelectric ceramic material with ultrahigh voltage coefficient and ultrahigh photoluminescence performance and preparation method thereof
Technical Field
The invention relates to a transparent photoelectric ceramic material with ultrahigh voltage coefficient and ultrahigh photoluminescence performance and a preparation method thereof, belonging to the technical field of photoelectric materials.
Background
The ferroelectric piezoelectric material is a material which has spontaneous polarization in crystal lattices and can be turned along with an electric field. Ferroelectric piezoelectric materials have a variety of useful physical effects such as piezoelectric effect, inverse piezoelectric effect, and electro-optical effect, and thus, such materials are widely used as core sensitive materials of functional devices such as sensors, transducers, micro-drivers, and electro-optical switches.
The ferroelectric material is doped with rare earth ions with luminous effect, so that the ferroelectric piezoelectric material has various physical effects of piezoelectricity, luminescence, electro-light and the like. Due to the fact that the materials have various physical effects, multi-effect synergy can be achieved. For example, the ceramic having both piezoelectric property and luminescent property can regulate the luminescent intensity by electric field, breaking through the limitation that the traditional luminescent material must rely on chemical concentration to regulate the luminescent intensity. Therefore, the multifunctional material has a very huge application prospect in novel optoelectronic devices.
Most of the materials with piezoelectric and luminescent properties currently studied are based on lead-free piezoelectric ceramics such as potassium-sodium niobate, sodium bismuth titanate or barium titanate ceramic systems, and the piezoelectric properties of the materials are weak, so that the efficiency of regulating and controlling the luminescent intensity by using the piezoelectric properties is low. If the ceramic with high piezoelectric performance and luminescent performance can be obtained, the luminous intensity regulation efficiency of the ceramic is certainly and greatly improved. Meanwhile, most of the ceramics developed at present are not transparent. For opaque ceramics, photoluminescence is limited on the surface of a sample, and the interior of the sample cannot participate in luminescence, so that the luminescence intensity is not high. If the ceramic can be made transparent by advanced preparation technology, the luminous intensity of the ceramic is necessarily greatly improved.
In view of the above, it is necessary to develop a transparent ferroelectric piezoelectric ceramic having high piezoelectric properties and high photoluminescent properties.
Disclosure of Invention
In order to solve the problems of low piezoelectric performance, opacity, low luminous intensity and the like of the prior ferroelectric piezoelectric material with photoluminescence characteristics, the invention provides a transparent photoelectric ceramic material with ultrahigh piezoelectric coefficient and ultrahigh photoluminescence performance and a preparation method thereof, so as to meet the performance requirements of preparing optical communication, solid luminescence and other novel optical devices.
On one hand, the invention provides a transparent photoelectric ceramic material with ultrahigh piezoelectric coefficient and superstrong photoluminescence performance, and the general formula of the composition of the transparent photoelectric ceramic material is as follows: pb1-yPry[(Mg1/3Nb2/3)1-xTix]1-y/4O3Wherein x is more than or equal to 0.28 and less than or equal to 0.35, and y is more than or equal to 0.005 and less than or equal to 0.04.
In the present invention, Pr3+The material can occupy A site (Pb site) in PMN-PT crystal lattice to form local inhomogeneous structure, so that more polar nanometer micro areas are introduced into the material, and the B site has vacancy for charge balance, and the transparent photoelectric ceramic material with superhigh piezoelectric coefficient and superhigh photoluminescence performance is finally obtained.
Preferably, x is more than or equal to 0.29 and less than or equal to 0.31, and y is more than or equal to 0.015 and less than or equal to 0.03.
Further, it is preferable that x be 0.30 and y be 0.02.
Preferably, the transparent photoelectric ceramic material has a linear transmittance of at least 50% (preferably at least 63%) in an infrared band (900-3000nm), and a quasi-static piezoelectric constant d33850 to 940pC/N (preferably 870 to 940), and an effective piezoelectric constant d33 *Is 1030 to 1270pm/V (preferably 1070 to 1270 pm/V).
Preferably, the transparent photoelectric ceramic material can emit red light with a wavelength of 650nm under the excitation of a wavelength of 450nm, and the luminous intensity of the transparent photoelectric ceramic material is (1.3-1.9) × 106The number of counts is preferably (1.4-1.8) × 106。
On the other hand, the invention also provides a preparation method of the transparent electro-optic ceramic material with the ultrahigh voltage coefficient and the ultrahigh photoluminescence performance, which comprises the following steps
(1) PbO powder and TiO2Powder, Pr6O11Powder and MgNb2O6The powder is used as raw material and has the composition formula of Pb1-yPry[(Mg1/3Nb2/3)1-xTix]1-y/4O3Weighing and mixing, and then calcining at 800-1000 ℃ to obtain praseodymium-doped PMN-PT ceramic powder;
(2) pressing and molding the obtained praseodymium-doped PMN-PT ceramic powder to obtain a ceramic biscuit; or mixing the praseodymium-doped PMN-PT ceramic powder with a binder, granulating, and performing compression molding and plastic removal to obtain a ceramic biscuit;
(3) and placing the obtained ceramic biscuit in an oxygen atmosphere, and carrying out hot-pressing sintering for 6-15 hours under the pressure of 30-100 MPa and at the temperature of 1050-1300 ℃ to obtain the transparent photoelectric ceramic material with the ultrahigh voltage coefficient and the ultrahigh photoluminescence performance.
Preferably, the MgNb is2O6The preparation method of the powder comprises the following steps: according to MgNb2O6General formula MgO and Nb were weighed2O5Mixing the raw materials, and calcining at 900-1200 ℃ to obtain MgNb2O6And (3) powder.
Preferably, the binder is at least one selected from a PVA solution with a concentration of 5wt% and a PVB solution, and the adding amount of the binder is 8-10 wt% of the mass of the praseodymium-doped PMN-PT ceramic powder.
Preferably, the pressure of the compression molding is 150-250 MPa.
In the invention, the Pr ion doped PMN-PT ceramic is sintered by hot pressing in an oxygen atmosphere, so that the ceramic is more compact, and the defects such as oxygen vacancy and the like are fewer, and the transmittance, the piezoelectric constant and the luminous intensity are greatly improved at the same time.
Has the advantages that:
compared with the prior art, the ceramic material provided by the invention has the linear transmittance of more than 63% in an infrared band without considering surface reflection loss, and the quasi-static piezoelectric constant d33Can reach 940pC/N, effective piezoelectric constant d33 *Can reach 1270 pm/V; the material can emit red light with the wavelength of 650nm under the excitation of the wavelength of 450nm, the luminous intensity of the material reaches more than 7 times of that of opaque ceramics, the material can meet the performance requirements of the material applied to optical communication, solid luminescence and other novel optical devices, and the material has the advantages ofHas wide application prospect. Moreover, the preparation method has the advantages of simple operation, short period, lower cost, easy large-scale production and the like.
Drawings
FIG. 1 is a photograph of a transparent ceramic obtained in example 1;
FIG. 2 is a graph showing transmittance of the ceramic material prepared in example 1;
FIG. 3 is an emission spectrum of the ceramic material prepared in example 1 under the excitation of a laser at 450 nm;
FIG. 4 is a unidirectional electrostrictive curve of the ceramic material obtained in example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the disclosure, the general formula of the transparent photoelectric ceramic material having both the ultra-high piezoelectric coefficient and the ultra-strong photoluminescence property may be: pb1-yPry[(Mg1/3Nb2/3)1-xTix]1-y/4O3Wherein: x and y are molar ratio, x is more than or equal to 0.28 and less than or equal to 0.35, and y is more than or equal to 0.005 and less than or equal to 0.04. The ceramic material provided by the invention is a transparent electro-optic ceramic material with ultrahigh piezoelectric coefficient and superstrong photoluminescence characteristic, and can meet the performance requirements of the ceramic material applied to novel optical devices such as sensors, drivers and solid light emitting devices.
In one embodiment of the invention, Pr-doped PMN-PT-based ceramic powder is prepared, and then hot-pressed and sintered in an oxygen atmosphere to promote pore closure, so that the transparent photoelectric ceramic material with ultrahigh piezoelectric coefficient and ultrahigh photoluminescence performance is finally obtained. The invention adopts a hot-pressing sintering process, and the transparency, piezoelectric constant and luminous intensity of the prepared ceramic are far higher than those of the existing reports. The following is an exemplary description of the preparation process of the transparent photoelectric ceramic material having ultra-high piezoelectric coefficient and ultra-strong photoluminescence performance.
According to MgNb2O6General formula MgO and Nb with accurate weighing of stoichiometric ratio2O5Ball milling, calcining,Ball milling step again to obtain MgNb2O6Ceramic powder. MgNb2O6The calcination temperature of the ceramic powder can be 900-1200 deg.C (e.g., 1000-1200 deg.C). MgNb2O6The calcination time of the ceramic powder can be 4-6 hours. In the ball milling and ball milling again process, deionized water or alcohol is used as a medium, the rotating speed is 300-350 r/min, and the planetary ball milling time is 2-6 hours.
According to (1-x) Pb1-yPry[(Mg1/3Nb2/3)1-xTix]1-y/4O3General formula of PbO and TiO with accurately weighed stoichiometric ratio2、Pr6O11And MgNb2O6And performing ball milling, calcining, ball milling again and the like on the ceramic powder to prepare the praseodymium-doped PMN-PT ceramic powder. The calcination temperature of the praseodymium-doped PMN-PT ceramic powder can be 900-1200 ℃, and the calcination time can be at least 1 hour. In the ball milling and ball milling again process, deionized water or alcohol is used as a medium, the rotating speed is 300-350 r/min, and the planetary ball milling time is 2-6 hours.
And pressing and forming the praseodymium-doped PMN-PT ceramic powder to obtain a ceramic biscuit. Or mixing praseodymium-doped PMN-PT ceramic powder with a binder, and then granulating to obtain granulated powder. The binder can be at least one of PVA (polyvinyl acetate) and PVB (polyvinyl butyral) solution with the concentration of 5%, and the adding amount of the binder is 8-10 wt% of the mass of the praseodymium-doped PMN-PT ceramic powder. And pressing and molding the granulated powder to obtain a ceramic blank. And performing plastic removal on the obtained ceramic blank to obtain a ceramic biscuit. Wherein the pressure for press molding is 200 MPa. The temperature of plastic removal can be 500-550 ℃, and the time can be 4-6 hours. The raw material may be dry-pressed into a cylinder having a diameter of 20 mm.
And putting the ceramic biscuit into a hot pressing furnace, and carrying out hot pressing sintering in an oxygen atmosphere to obtain the transparent photoelectric ceramic material with the ultrahigh voltage coefficient and the ultrahigh photoluminescence performance. Wherein the hot-pressing sintering is carried out at 1050-1300 ℃ and 30-100 MPa for 6-15 hours.
In the invention, the transparent photoelectric ceramic material obtained by adopting an ultraviolet-visible-infrared spectrophotometer Cary 5000 test can reach more than 50% of linear transmittance in an infrared band (900-3000nm) without considering surface reflection loss.
In the present invention, a quasi-static d is adopted33Quasi-static piezoelectric constant d of transparent photoelectric ceramic material obtained by tester ZJ-3AN33Can reach 940 pC/N.
In the present invention, the effective piezoelectric constant d of the transparent photoelectric ceramic material obtained by using the ferroelectric/piezoelectric analyzer TF2000E33 *Can reach 1270 pm/V.
In the invention, the transparent photoelectric ceramic material obtained by a fluorescence spectrometer Hitachi F-4500 test can emit the luminous intensity of red light with the wavelength of 650nm under the excitation of the wavelength of 450nm, and the luminous intensity of the transparent photoelectric ceramic material reaches more than 7 times of that of opaque ceramic.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
(1) According to MgNb2O6General formula MgO and Nb with accurate weighing of stoichiometric ratio2O5Adopting deionized water or alcohol as medium, planetary ball milling for 6 hours, calcining for 4 hours at 1100 ℃, adopting deionized water or alcohol as medium again, planetary ball milling for 6 hours, and obtaining MgNb2O6Ceramic powder;
(2) according to Pb1-yPry[(Mg1/3Nb2/3)1-xTix]1-y/4O3In general formula (I), where x is 0.30 and y is 0.02, PbO and TiO are precisely weighed in stoichiometric ratio2、Pr6O11Adding the MgNb prepared in the step a)2O6In the ceramic powder body deionized water is adoptedOr alcohol is taken as a medium, the mixture is subjected to planetary ball milling for 6 hours, calcined at 850 ℃, deionized water or alcohol is taken as a medium again, subjected to planetary ball milling for 6 hours, and dried to prepare praseodymium-doped lead magnesium niobate titanate ceramic powder;
(3) adding 8 wt% PVA solution, granulating, dry-pressing under 200MPa to obtain 20mm diameter cylinder, and removing plastics (550 deg.C, 4 hr);
(4) sintering by a hot pressing method: the pressure sintering is carried out for 6 hours at 1240 ℃ and 50 MPa.
FIG. 1 is a photograph showing a ceramic material prepared in example 1. As can be seen from fig. 1, the praseodymium-doped ceramic exhibits a light green color, while the ceramic has good transparency characteristics.
FIG. 2 is a graph showing the linear transmittance of the ceramic material prepared in example 1. As can be seen from FIG. 2, the optical transmittance of the prepared ceramic material can reach 63% in-line transmittance in the infrared band without considering surface reflection loss, and the ceramic material has high transmittance.
FIG. 3 is a graph showing the emission spectrum of the ceramic material obtained in example 1 under 450nm excitation. As can be seen from FIG. 3, the prepared ceramic material emits strong red light with a wavelength of 650nm under the excitation of 450nm, and the luminous intensity can reach 1.4 × 106Counting, and compared with the opaque ceramic with the same component, the luminous intensity is improved by 7 times.
FIG. 4 is a unidirectional electrostrictive curve of the ceramic material obtained in example 1. As can be seen from FIG. 4, the prepared ceramic material has ultra-high electrostriction and equivalent piezoelectric coefficient d33 *Up to 1270pm/V, its quasi-static piezoelectric constant d33940pC/N is reached.
Example 2
(1) According to MgNb2O6General formula MgO and Nb with accurate weighing of stoichiometric ratio2O5Adopting deionized water or alcohol as medium, planetary ball milling for 6 hours, calcining for 4 hours at 1100 ℃, adopting deionized water or alcohol as medium again, planetary ball milling for 6 hours, and obtaining MgNb2O6Ceramic powder;
(2) according to Pb1-yPry[(Mg1/3Nb2/3)1-xTix]1-y/4O3In general formula (I), where x is 0.29 and y is 0.03, PbO and TiO are precisely weighed in stoichiometric ratio2、Pr6O11Adding the MgNb prepared in the step a)2O6In the ceramic powder, deionized water or alcohol is used as a medium, planetary ball milling is carried out for 6 hours, the ceramic powder is calcined at 850 ℃, deionized water or alcohol is used as a medium again, planetary ball milling is carried out for 6 hours, and drying is carried out to prepare praseodymium-doped lead magnesium niobium titanate ceramic powder;
(3) adding 8 wt% PVA solution as binder, granulating, dry-pressing under 200MPa to obtain 20mm diameter cylinder, and removing plastics (500 deg.C, 4 hr);
(4) sintering by a hot pressing method: the pressure sintering is carried out for 10 hours at 1240 ℃ and 50 MPa.
Detection and analysis show that the ceramic material prepared in the embodiment 2 has a linear transmittance of 65% in an infrared band without considering surface reflection loss, can emit red light with a wavelength of 650nm under the excitation of a wavelength of 450nm, and has a luminous intensity of 1.8 × 106Counting; its equivalent piezoelectric coefficient d33 *Up to 1070pm/V, its quasi-static piezoelectric constant d33To 870 pC/N.
Example 3
The process for preparing the transparent photoelectric ceramic material in the embodiment 3 is as follows with reference to the embodiment 1, except that: x is 0.28 and x is 0.02. Detection and analysis show that the ceramic material prepared in the embodiment 3 has the linear transmittance of 66% in an infrared band without considering the surface reflection loss, can emit red light with the wavelength of 650nm under the excitation of the wavelength of 450nm, and has the luminous intensity of 1.5 multiplied by 106Counting; its equivalent piezoelectric coefficient d33 *Up to 1020pm/V, its quasi-static piezoelectric constant d33850pC/N is achieved.
Example 4
The process for preparing the transparent photoelectric ceramic material in the embodiment 4 is as follows with reference to the embodiment 1, except that: x is 0.35 and y is 0.02. The detection and analysis show that the linear transmittance of the ceramic material prepared in the embodiment 4 in the infrared band can reach 58% without considering the surface reflection loss, and the ceramic material is excited at the wavelength of 450nmCan emit red light with a wavelength of 650nm under the action of light, and the luminous intensity can reach 1.9 multiplied by 106Counting; its equivalent piezoelectric coefficient d33 *Up to 960pm/V, its quasi-static piezoelectric constant d331050pC/N is reached.
Example 5
The process for preparing the transparent photoelectric ceramic material in the embodiment 5 is as follows with reference to the embodiment 1, except that: x is 0.30 and y is 0.04. Detection and analysis show that the ceramic material prepared by the embodiment has the linear transmittance of 64% in an infrared band without considering surface reflection loss, can emit red light with the wavelength of 650nm under the excitation of the wavelength of 450nm, and has the luminous intensity of 1.3 multiplied by 106Counting; its equivalent piezoelectric coefficient d33 *Up to 1108pm/V, its quasi-static piezoelectric constant d33Reach 1030 pC/N.
Comparative example 1
(1) According to MgNb2O6General formula MgO and Nb with accurate weighing of stoichiometric ratio2O5Adopting deionized water or alcohol as medium, planetary ball milling for 6 hours, calcining for 4 hours at 1100 ℃, adopting deionized water or alcohol as medium again, planetary ball milling for 6 hours, and obtaining MgNb2O6Ceramic powder;
(2) according to Pb1-yPry[(Mg1/3Nb2/3)1-xTix]1-y/4O3In general formula (I), where x is 0.30 and y is 0.02, PbO and TiO are precisely weighed in stoichiometric ratio2、Pr6O11Adding the MgNb prepared in the step a)2O6In the ceramic powder, deionized water or alcohol is used as a medium, planetary ball milling is carried out for 6 hours, the ceramic powder is calcined at 850 ℃, deionized water or alcohol is used as a medium again, planetary ball milling is carried out for 6 hours, and drying is carried out to prepare praseodymium-doped lead magnesium niobium titanate ceramic powder;
(3) adding 8 wt% of PVA solution binder, granulating, drying and pressing under 200MPa to obtain a wafer with the diameter of 20mm, and removing plastics (550 ℃ for 4 hours);
(4) carrying out common sintering: the sample is put into a high-temperature sintering furnace to be sintered for 6 hours at 1240 ℃ in air atmosphere, and the detection and analysis show that the sample is prepared byThe ceramic material prepared in comparative example 1 has a linear transmittance close to 0 in an infrared band without considering surface reflection loss, can emit red light with a wavelength of 650nm under the excitation of a wavelength of 450nm, and has a luminous intensity of 2.1 × 105Counting; its equivalent piezoelectric coefficient d33 *Up to 920pm/V, its quasi-static piezoelectric constant d33670pC/N is achieved.
Comparative example 2
The process for preparing the transparent photovoltaic ceramic material in this comparative example 2 is referred to example 1, except that: x is 0.30 and y is 0. Detection and analysis show that the linear transmittance of the ceramic material prepared in the comparative example 2 in an infrared band is only about 30% when the surface reflection loss is not considered, and the ceramic material has no photoluminescence effect under the excitation of a wavelength of 450 nm; its equivalent piezoelectric coefficient d33 *670pm/V only, its quasi-static piezoelectric constant d33Only 480 pC/N.
In conclusion, the transparent ceramic material provided by the invention has the linear transmittance of more than 50% in the infrared band without considering the surface reflection loss, and the quasi-static piezoelectric constant d33Over 850pC/N, effective piezoelectric constant d33 *Over 1000 pm/V; the material can emit red light with the wavelength of 650nm under the excitation of the wavelength of 450nm, the luminous intensity of the material is far higher than that of opaque ceramic with the same composition, and the material is novel transparent photoelectric ceramic with ultrahigh piezoelectric performance and ultrahigh photoluminescence performance.
It is necessary to point out here: the above examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential modifications and adaptations of the present invention by those skilled in the art based on the foregoing descriptions are within the scope of the present invention.

Claims (8)

1. A transparent photoelectric ceramic material with ultrahigh piezoelectric coefficient and ultrahigh photoluminescence performance is characterized in that the general formula of the composition of the transparent photoelectric ceramic material is as follows: pb1-yPry[(Mg1/3Nb2/3)1-xTix]1-y/4O3Wherein x is more than or equal to 0.28 and less than or equal to 0.35,0.005≤y≤0.04。
2. the transparent electro-optic ceramic material of claim 1 wherein x is 0.29. ltoreq. x.ltoreq.0.31, y is 0.015. ltoreq. y.ltoreq.0.03; preferably, x =0.30 and y = 0.02.
3. The transparent electro-optic ceramic material of claim 1 or 2, wherein the transparent electro-optic ceramic material has an in-line transmittance of at least 50% in the infrared band and a quasi-static piezoelectric constant d33850 to 940pC/N, effective piezoelectric constant d33 *1030 to 1270 pm/V.
4. The transparent electro-optic ceramic material according to any one of claims 1-3, wherein the transparent electro-optic ceramic material can emit red light with a wavelength of 650nm under the excitation of a wavelength of 450nm, and the emission intensity is (1.3-1.9) x 106And (6) counting.
5. A method for preparing the transparent electro-optic ceramic material with ultrahigh piezoelectric coefficient and ultrahigh photoluminescence performance according to any one of claims 1 to 4, which comprises
(1) PbO powder and TiO2Powder, Pr6O11Powder and MgNb2O6The powder is used as raw material and has the composition formula of Pb1-yPry[(Mg1/3Nb2/3)1-xTix]1-y/4O3Weighing and mixing, and then calcining at 800-1000 ℃ to obtain praseodymium-doped PMN-PT ceramic powder;
(2) pressing and molding the obtained praseodymium-doped PMN-PT ceramic powder to obtain a ceramic biscuit; or mixing the praseodymium-doped PMN-PT ceramic powder with a binder, granulating, and performing compression molding and plastic removal to obtain a ceramic biscuit;
(3) and placing the obtained ceramic biscuit in an oxygen-containing atmosphere, and carrying out hot-pressing sintering for 6-15 hours under the pressure of 30-100 MPa and at the temperature of 1050-1300 ℃ to obtain the transparent photoelectric ceramic material with the ultrahigh voltage coefficient and the ultrahigh photoluminescence performance.
6. The method according to claim 5, wherein the MgNb is2O6The preparation method of the powder comprises the following steps: according to MgNb2O6General formula MgO and Nb were weighed2O5Mixing the raw materials, and calcining at 900-1200 ℃ to obtain MgNb2O6And (3) powder.
7. The process of claim 5 or 6, wherein the binder is at least one selected from the group consisting of a PVA solution and a PVB solution, the concentration of the PVA solution and the PVB solution being 5 wt%; the addition amount of the PVA solution and the PVB solution is 8-10 wt% of the mass of the praseodymium-doped PMN-PT ceramic powder.
8. The production method according to any one of claims 5 to 7, wherein the pressure for press molding is 150 to 250 MPa.
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