CN115073159B - Bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance and low-temperature oxygen-containing hot pressed sintering preparation method thereof - Google Patents
Bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance and low-temperature oxygen-containing hot pressed sintering preparation method thereof Download PDFInfo
- Publication number
- CN115073159B CN115073159B CN202210912495.XA CN202210912495A CN115073159B CN 115073159 B CN115073159 B CN 115073159B CN 202210912495 A CN202210912495 A CN 202210912495A CN 115073159 B CN115073159 B CN 115073159B
- Authority
- CN
- China
- Prior art keywords
- ceramic
- temperature
- equal
- tio
- sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—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
- C04B35/26—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 ferrites
- C04B35/2608—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead
- C04B35/2616—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead containing lithium
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—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
- C04B35/26—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 ferrites
- C04B35/2608—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead
- C04B35/2633—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead containing barium, strontium or calcium
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—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
- C04B35/46—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 titanium oxides or titanates
- C04B35/462—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 titanium oxides or titanates based on titanates
- C04B35/465—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 titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—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 titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3258—Tungsten oxides, tungstates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention discloses bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance and a low-temperature oxygen-containing hot-pressed sintering preparation method thereof, wherein the ceramic has the following composition general formula: (1-u)BiFeO 3 ‑uBaTiO 3 +1.0mol%MnCO 3 +xmol%(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 +ymol%Ba(W 1/2 Cu 1/2 )O 3 +zmol%B 2 O 3 Whereinu、x、yAndzrepresents the mole fraction, (Bi) 0.5 Na 0.25 Li 0.25 )TiO 3 、Ba(W 0.5 Cu 0.5 )O 3 B (B) 2 O 3 Is a low-temperature sintering auxiliary agent and is more than or equal to 0.20 percentu≤0.45，0＜x≤2.0，0≤y≤5.0，0≤zLess than or equal to 5.0. The method can be used for sintering the porcelain under the conditions of 820-920 ℃ and 25Mpa pressure and oxygen-containing atmosphere by adding the sintering aid. The invention reduces the sintering temperature of bismuth ferrite-barium titanate ceramic, reduces volatilization of Bi element, improves the density of the ceramic, reduces dielectric loss of the ceramic, and obtains the lead-free piezoelectric ceramic with high piezoelectric performance, high Curie temperature and low dielectric loss.
Description
Technical Field
The invention relates to lead-free piezoelectric ceramics and a low-temperature hot-pressing sintering preparation technology, in particular to bismuth ferrite-barium titanate ceramics with high Curie temperature and high piezoelectric performance and a low-temperature oxygen-containing hot-pressing sintering preparation method thereof.
Background
The piezoelectric ceramic has wide application in the high-tech fields such as aerospace, nuclear power, petrochemical industry, geological exploration, metallurgy, automobile fuel monitoring, 3D printing, high-temperature ultrasonic application and the like. At present, lead zirconate titanate (PZT) and a modified piezoelectric ceramic system thereof are mainly applied in the field, so that the sintering temperature of the ceramic is reduced by adopting various sintering aids for saving energy and reducing production cost, and meanwhile, a lower sintering temperature of the multilayer piezoelectric ceramic is also expected for reducing the cost of an internal electrode. At present, the sintering temperature of a lead zirconate titanate system is reduced to about 950 ℃, but the lead volatilization problem still exists in the preparation of the multilayer piezoelectric ceramic by sintering at the temperature, and the environment is seriously polluted, so that the lead-free piezoelectric ceramic has important social significance.
BiFeO 3 -BaTiO 3 The ceramic has the excellent characteristics of high Curie temperature, low sintering temperature, no toxicity and perovskite structure, however, during the sintering process, due to BiFeO 3 With BaTiO 3 The sintering temperature difference of the ceramic is too large, namely 830 ℃ and 1400 ℃, and the ceramic is insufficient and cannot be polarized if the sintering temperature is too low. The Bi element is seriously volatilized when the sintering temperature is too high. In order to balance valence, bi element volatilization can cause a large number of oxygen vacancies, lattice defects and holes in ceramic, so that the dielectric loss of the system is high and cannot be polarized, after Mn element doping modification is added, the resistivity of the system is effectively improved, the dielectric loss is reduced, but the dielectric loss is still higher (more than or equal to 5 percent), thus reducing BiFeO 3 -BaTiO 3 The dielectric loss of ceramics can be worked from the aspects of reducing sintering temperature and improving ceramic density.
Patent publication No. CN102584195A discloses a bismuth-based perovskite type leadless piezoelectric ceramic and a low-temperature preparation method thereof, wherein a solid phase synthesis sintering method by adding a low-temperature sintering auxiliary agent is adopted to successfully reduce the sintering temperature to about 900 ℃, but the problems of volatilization of bismuth element and higher dielectric loss are still not solved.
Hot press sintering is a common ceramic preparation method, however, because a hot press mold resistant to high temperature is required, hot press sintering is required to be sintered under an oxygen-free protective atmosphere. In BiFeO 3 -BaTiO 3 In the preparation process of the system ceramic, the system is extremely easy to generate oxygen vacancies in the sintering process, so that the system cannot be sintered in an oxygen-free atmosphere.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance and a low-temperature oxygen-containing hot-pressed sintering preparation method thereof, so as to reduce BiFeO 3 -BaTiO 3 The sintering temperature of the system ceramic reduces the volatilization of Bi element, improves the Curie temperature and high temperature stability of the system ceramic, and obtains BiFeO with high piezoelectric performance, high Curie temperature and low dielectric loss 3 -BaTiO 3 Lead-free piezoelectric ceramics.
The technical scheme for realizing the aim of the invention is as follows:
bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance, wherein the ceramic has the following composition general formula:
(1-u)BiFeO 3 -uBaTiO 3 +1.0mol％MnCO 3 +xmol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 +ymol％Ba(W 1/2 Cu 1/2 )O 3 +zmol％B 2 O 3 wherein u, x, y and z represent mole fractions, (Bi) 0.5 Na 0.25 Li 0.25 )TiO 3 、Ba(W 0.5 Cu 0.5 )O 3 B (B) 2 O 3 Is a low-temperature sintering auxiliary agent, and u is more than or equal to 0.20 and less than or equal to 0.45,0, x is more than or equal to 0 and less than or equal to 2.0, y is more than or equal to 0 and less than or equal to 5.0,0, and z is more than or equal to 5.0.
The preparation method of the bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance by low-temperature oxygen-containing hot-pressed sintering comprises the following steps:
1) To analyze pure Fe 2 O 3 、Bi 2 O 3 、Li 2 CO 3 、Na 2 CO 3 、TiO 2 And nano BaTiO 3 The powder is used as raw material and is prepared according to (1-u) BiFeO 3 -uBaTiO 3 +xmol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 Mixing materials, wherein u is more than or equal to 0.20 and less than or equal to 0.45,0 and x is less than or equal to 2.0, ball milling for 24 hours by taking absolute ethyl alcohol as a medium, taking out, drying for 12 hours at 100 ℃, sieving with 200-250 meshes, putting into a high-aluminum crucible, compacting, capping, heating to 750 ℃ at a heating rate of 250 ℃/h, and preserving heat for 6 hours for synthesis for later use;
2) To analytically pure BaCO 3 、WO 3 And CuO as raw materials according to Ba (Cu) 1/2 W 1/2 )O 3 Proportioning in chemical formula, mixing, ball milling for 24 hours, taking out, drying, sieving with 200-250 meshes, putting into a high-aluminum crucible, pressing and capping, heating to 850 ℃ at a heating rate of 250 ℃/h, and preserving heat for 6 hours for synthesis for later use;
3) The (1-u) BiFeO synthesized in the step 1) is reacted with 3 -uBaTiO 3 +xmol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 And step 2) synthesized Ba (Cu) 1/2 W 1/2 )O 3 Powder and B 2 O 3 MnCO 3 According to (1-u) BiFeO 3 -uBaTiO 3 +1.0mol％MnCO 3 +xmol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 +ymol％Ba(Cu 1/2 W 1/2 )O 3 +zmol％B 2 O 3 Proportioning, wherein u is more than or equal to 0.20 and less than or equal to 0.45,0, x is more than or equal to 0 and less than or equal to 2.0, y is more than or equal to 0 and less than or equal to 5.0,0, z is more than or equal to 5.0, taking absolute ethyl alcohol as a medium, ball milling for 24 hours, taking out, drying, and sieving with a 200-250 mesh sieve for later use;
4) Placing the powder synthesized in the step 3) into a hot-pressing sintering machine, adopting an alumina corundum mold, directly heating to 100 ℃ at a speed of 5 ℃/min under the air or pure oxygen atmosphere condition, preserving heat for 15min to remove water vapor in the powder, rapidly heating to a sintering temperature of 820-920 ℃ at a heating speed of 20 ℃/min, keeping the temperature unchanged, starting to pressurize to 25Mpa, preserving heat and pressure for 30min, powering off, cooling with boiled water, and rapidly cooling to room temperature;
5) Cutting the sintered sample into ceramic plates with different sizes according to the requirements, and polishing and processing the ceramic plates into thin plates with smooth two sides and thickness of 0.5-1.0mm, and coating silver electrodes;
6) Polarizing the fired piezoelectric ceramic sheet in silicone oil, polarizing the electric field at 6000V/mm, maintaining the temperature at 120 ℃ for 30min, maintaining the electric field and cooling to room temperature.
The invention adopts an alumina corundum mould and simultaneously uses BiFeO 3 -BaTiO 3 Sintering aid Ba (W) is added into the powder 1/ 2 Cu 1/2 )O 3 、(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 、B 2 O 3 Reducing sintering temperature, hot-pressing and sintering the system under pure oxygen atmosphere or oxygen-containing atmosphere, and reducing the minimum hot-pressing and sintering temperature to 820 ℃ while utilizing (Bi) 0.5 Na 0.25 Li 0.25 )TiO 3 The low tolerance factor characteristic of the system improves the Curie temperature and the high temperature stability of the system, and finally the BiFeO with high piezoelectric property, high Curie temperature and low dielectric loss is obtained 3 -BaTiO 3 Lead-free piezoelectric ceramics.
The invention has the following positive effects:
(1) The technical proposal fully utilizes Ba (Cu) 1/2 W 1/2 )O 3 And (Bi) 0.5 Na 0.25 Li 0.25 )TiO 3 And (1-u) BiFeO 3 -uBaTiO 3 Form a good solid solution by adding B with a low melting point 2 O 3 Forming a low-temperature liquid phase in the sintering process, greatly reducing the hot-pressing sintering temperature of the system to 820 ℃, promoting grain boundary movement and grain growth, and obtaining the piezoelectric ceramic with uniform grain growth; on the other hand, the method utilizes (Bi 0.5 Na 0.25 Li 0.25 )TiO 3 The Curie temperature and the high-temperature stability of the system are improved due to the low tolerance factor of the system;
(2) The hot-pressing sintering is performed in a closed space, so that volatilization of Bi element can be effectively prevented, holes and oxygen vacancies can be reduced, meanwhile, the density of the ceramic is improved by hot-pressing, lattice defects are reduced, and dielectric loss of the ceramic is reduced;
(3) The hot pressed sintering is completed under the condition of oxygen-containing atmosphere, and BiFeO can be effectively avoided 3 -BaTiO 3 The ceramic generates oxygen vacancies in the hot-pressing sintering process, and adopts water cooling to forcedly and rapidly cool down when cooling down, thereby reducing the time of cooling down stage and being beneficial to reducing the generation of intermediate phase.
The invention successfully adds the sintering auxiliary agent and the hot pressing process to prepare the (1-u) BiFeO 3 -uBaTiO 3 +1.0mol％MnCO 3 The sintering temperature of the ceramic is reduced from 960 ℃ to 820-920 ℃, the relative density of the system is improved from 95% to 99% while the sintering temperature is reduced, and the piezoelectric ceramic sample with high Curie temperature, high piezoelectric performance and low dielectric loss is obtained, and has excellent piezoelectric performance and high temperature stability. The in-situ dynamic depolarization test result of the sample prepared in the embodiment 1 shows that, as shown in the attached figure 1, the piezoelectric ceramic prepared by the technology of the invention has the application temperature range of more than 300 ℃, the piezoelectric property of 498pC/N at the highest temperature of 315 ℃, compared with the prior art, the piezoelectric ceramic material with the piezoelectric property exceeding 300pC/N does not exist at the high temperature, so the ceramic prepared by the technology of the invention has great breakthrough and innovation.
Drawings
FIG. 1 is a graph showing in-situ dynamic depolarization of the ceramic prepared in example 1 of the present invention.
Detailed Description
The present disclosure is further illustrated by the following examples and figures, where the examples described are merely some, but not all, examples of the invention. 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 be within the scope of the invention.
Example 1:
bismuth ferrite-barium titanate ceramic with high curie temperature and high piezoelectric properties, wherein the chemical formula of the ceramic is as follows: 0.68BiFeO 3 -0.32BaTiO 3 +1.0mol％MnCO 3 +1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 +2.5mol％B 2 O 3 +
3.0mol％Ba(Cu 1/2 W 1/2 )O 3 ，
The preparation method of the ceramic by low-temperature oxygen-containing hot-pressed sintering comprises the following steps:
(1) To analyze pure Fe 2 O 3 、Bi 2 O 3 、Li 2 CO 3 、Na 2 CO 3 、TiO 2 And nano BaTiO 3 The powder is used as raw material according to 0.68BiFeO 3 -0.32BaTiO 3 +1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 Proportioning, ball milling for 24 hours by taking absolute ethyl alcohol as a medium, taking out, drying at 100 ℃ for 12 hours, sieving with a 200-mesh sieve, putting into a high-aluminum crucible for compaction, capping, heating to 750 ℃ at a heating rate of 250 ℃/h, and preserving heat for 6 hours for synthesis for later use;
(2) To analytically pure BaCO 3 、WO 3 And CuO as raw materials according to Ba (Cu) 1/2 W 1/2 )O 3 Proportionally mixing the materials in the chemical formula, ball milling for 24 hours, taking out, drying, sieving with 200 meshes, putting into a high-aluminum crucible, pressing and capping, heating to 850 ℃ at the heating rate of 250 ℃/h, and preserving heat for 6 hours for synthesis for later use;
(3) 0.68BiFeO synthesized in the step (1) 3 -0.32BaTiO 3 +1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 And Ba (Cu) synthesized in step (2) 1/2 W 1/2 )O 3 Powder and B 2 O 3 MnCO 3 According to 0.68BiFeO 3 -0.32BaTiO 3 +1.0mol％MnCO 3 +1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 +3.0mol％Ba(Cu 1/2 W 1/2 )O 3 +2.5mol％B 2 O 3 Batching, taking absolute ethyl alcohol as a medium, ball milling for 24 hours, taking out, drying and sieving with 200 meshes for standby;
(4) Placing the powder synthesized in the step (3) into a hot-pressing sintering machine, adopting an alumina corundum mold, directly heating to 100 ℃ at a heating rate of 5 ℃/min under the air or pure oxygen atmosphere condition, preserving heat for 15min to remove water vapor in the powder, heating to a sintering temperature of 880 ℃ at a heating rate of 20 ℃/min, preserving heat, gradually pressurizing to 25Mpa, preserving heat and pressure for 30min, powering off, cooling with boiled water, and rapidly cooling to room temperature;
(5) Cutting the sintered sample into ceramic plates with different sizes according to the requirements, polishing and processing the ceramic plates into thin plates with smooth two sides and thickness of 1.0mm, wherein the thin plates are in a coin shape or a cuboid shape and are coated with silver electrodes;
(6) Polarizing the fired piezoelectric ceramic sheet in silicone oil, polarizing the electric field at 6000V/mm, maintaining the temperature at 120 ℃ for 30min, maintaining the electric field and cooling to room temperature.
The performance measurements were as follows:
| d 33 (pC/N) | Q m | k p | ε r | Tanδ(％) | T c (℃) | T d (℃) |
| 498 | 74 | 0.32 | 665 | 1.53 | 523 | 490 |
the in-situ dynamic depolarization test result of the sample prepared in the embodiment 1 shows that the piezoelectric ceramic prepared by the technology of the invention can reach the application temperature range of more than 300 ℃ and the piezoelectric property of 498pC/N at the highest temperature of 315 ℃ as shown in the attached figure 1.
Example 2:
bismuth ferrite-barium titanate ceramic with high curie temperature and high piezoelectric properties, wherein the chemical formula of the ceramic is as follows:
0.70BiFeO 3 -0.30BaTiO 3 +1.0mol％MnCO 3 +2.0mol％Ba(Cu 1/2 W 1/2 )O 3 +2.5mol％B 2 O 3 +
1.5mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 ，
the preparation method of the ceramic by low-temperature oxygen-containing hot-pressed sintering is the same as in example 1, except that the sintering temperature in the step (4) is 870 ℃.
The performance measurements were as follows:
| d 33 (pC/N) | Q m | k p | ε r | Tanδ(％) | T c (℃) | T d (℃) |
| 466 | 68 | 0.34 | 647 | 1.38 | 556 | 525 |
example 3:
bismuth ferrite-barium titanate ceramic with high curie temperature and high piezoelectric properties, wherein the chemical formula of the ceramic is as follows:
0.65BiFeO 3 -0.35BaTiO 3 +1.0mol％MnCO 3 +1.0mol％Ba(Cu 1/2 W 1/2 )O 3 +2.5mol％B 2 O 3 +
1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 ；
the preparation method of the ceramic by low-temperature oxygen-containing hot-pressed sintering is the same as in example 1, except that the sintering temperature of step (4) is 920 ℃. The performance measurements were as follows:
| d 33 (pC/N) | Q m | k p | ε r | Tanδ(％) | T c (℃) | T d (℃) |
| 418 | 50 | 0.28 | 781 | 1.95 | 473 | 445 |
example 4:
bismuth ferrite-barium titanate ceramic with high curie temperature and high piezoelectric properties, wherein the chemical formula of the ceramic is as follows:
0.75BiFeO 3 -0.25BaTiO 3 +1.0mol％MnCO 3 +2.0mol％Ba(Cu 1/2 W 1/2 )O 3 +1.0mol％B 2 O 3 +
1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 ；
the preparation method of the ceramic by low-temperature oxygen-containing hot-pressed sintering is the same as in example 1, except that the sintering temperature in the step (4) is 820 ℃.
The performance measurements were as follows:
| d 33 (pC/N) | Q m | k p | ε r | Tanδ(％) | T c (℃) | T d (℃) |
| 407 | 39 | 0.31 | 583 | 0.96 | 590 | 545 |
the upper and lower limits and interval values of the components and the upper and lower limits and interval values of the process parameters listed in the above examples can be all achieved, and the present invention is not limited to the above examples.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (7)
1. The bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance is characterized by comprising the following components in percentage by weight:
(1-u)BiFeO 3 -uBaTiO 3 +1.0mol％MnCO 3 +xmol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 +ymol％Ba(W 1/ 2 Cu 1/2 )O 3 +zmol％B 2 O 3 wherein u, x, y and z represent mole fractions, (Bi) 0.5 Na 0.25 Li 0.25 )TiO 3 、Ba(W 0.5 Cu 0.5 )O 3 B (B) 2 O 3 Is a low-temperature sintering auxiliary agent, u is more than or equal to 0.20 and less than or equal to 0.45,0, x is more than or equal to 0 and less than or equal to 2.0, y is more than or equal to 0 and less than or equal to 5.0,0, and z is more than or equal to 5.0.
2. The method for preparing the bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance by low-temperature oxygen-containing hot-pressed sintering according to claim 1, which is characterized by comprising the following steps:
1) To analyze pure Fe 2 O 3 、Bi 2 O 3 、Li 2 CO 3 、Na 2 CO 3 、TiO 2 And nano BaTiO 3 The powder is used as raw material and is prepared according to (1-u) BiFeO 3 -uBaTiO 3 +xmol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 Mixing materials, wherein u is more than or equal to 0.20 and less than or equal to 0.45,0 and x is less than or equal to 2.0, ball milling for 24 hours by taking absolute ethyl alcohol as a medium, taking out, drying for 12 hours at 100 ℃, sieving with 200-250 meshes, putting into a high-aluminum crucible, compacting, capping, heating to 750 ℃ at a heating rate of 250 ℃/h, and preserving heat for 6 hours for synthesis for later use;
2) To analytically pure BaCO 3 、WO 3 And CuO as raw materials according to Ba (Cu) 1/2 W 1/2 )O 3 Proportioning in chemical formula, mixing, ball milling for 24 hours, taking out, drying, sieving with 200-250 meshes, putting into a high-aluminum crucible, pressing and capping, heating to 850 ℃ at a heating rate of 250 ℃/h, and preserving heat for 6 hours for synthesis for later use;
3) The (1-u) BiFeO synthesized in the step 1) is reacted with 3 -uBaTiO 3 +xmol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 And step 2) synthesized Ba (Cu) 1/2 W 1/2 )O 3 Powder and B 2 O 3 MnCO 3 According to (1-u) BiFeO 3 -uBaTiO 3 +1.0mol％MnCO 3 +xmol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 +ymol％Ba(Cu 1/2 W 1/2 )O 3 +zmol％B 2 O 3 Proportioning, wherein u is more than or equal to 0.20 and less than or equal to 0.45,0, x is more than or equal to 0 and less than or equal to 2.0, y is more than or equal to 0 and less than or equal to 5.0,0, z is more than or equal to 5.0, taking absolute ethyl alcohol as a medium, ball milling for 24 hours, taking out, drying, and sieving with 200-250 meshes for standby;
4) Placing the powder synthesized in the step 3) into a hot-pressing sintering machine, adopting an alumina corundum mold, directly heating to 100 ℃ at a speed of 5 ℃/min under the air or pure oxygen atmosphere condition, preserving heat for 15min to remove water vapor in the powder, rapidly heating to a sintering temperature of 820-920 ℃ at a heating speed of 20 ℃/min, keeping the temperature unchanged, starting to pressurize to 25Mpa, preserving heat and pressure for 30min, powering off, cooling with boiled water, and rapidly cooling to room temperature;
5) Cutting the sintered sample into ceramic plates with different sizes according to the requirements, and polishing and processing the ceramic plates into thin plates with smooth two sides and thickness of 0.5-1.0mm, and coating silver electrodes;
6) Polarizing the fired piezoelectric ceramic sheet in silicone oil, polarizing the electric field at 6000V/mm, maintaining the temperature at 120 ℃ for 30min, maintaining the electric field and cooling to room temperature.
3. The bismuth ferrite-barium titanate ceramic having high curie temperature and high piezoelectric properties according to claim 1, wherein the ceramic has a chemical formula of:
0.68BiFeO 3 -0.32BaTiO 3 +1.0mol％MnCO 3 +1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 +2.5mol％B 2 O 3 +3.0mol％Ba(Cu 1/2 W 1/2 )O 3 。
4. the method for preparing bismuth ferrite-barium titanate ceramics with high curie temperature and high piezoelectric property by low temperature oxygen-containing hot press sintering according to claim 3, comprising the steps of:
(1) To analyze pure Fe 2 O 3 、Bi 2 O 3 、Li 2 CO 3 、Na 2 CO 3 、TiO 2 And nano BaTiO 3 The powder is used as raw material according to 0.68BiFeO 3 -0.32BaTiO 3 +1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 Proportioning, ball milling for 24 hours by taking absolute ethyl alcohol as a medium, taking out, drying at 100 ℃ for 12 hours, sieving with a 200-mesh sieve, putting into a high-aluminum crucible for compaction, capping, heating to 750 ℃ at a heating rate of 250 ℃/h, and preserving heat for 6 hours for synthesis for later use;
(2) To analytically pure BaCO 3 、WO 3 And CuO as raw materials according to Ba (Cu) 1/2 W 1/2 )O 3 Proportionally mixing the materials in the chemical formula, ball milling for 24 hours, taking out, drying, sieving with 200 meshes, putting into a high-aluminum crucible, pressing and capping, heating to 850 ℃ at the heating rate of 250 ℃/h, and preserving heat for 6 hours for synthesis for later use;
(3) 0.68BiFeO synthesized in the step (1) 3 -0.32BaTiO 3 +1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 And Ba (Cu) synthesized in step (2) 1/2 W 1/2 )O 3 Powder and B 2 O 3 MnCO 3 According to 0.68BiFeO 3 -0.32BaTiO 3 +1.0mol％MnCO 3 +1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 +3.0mol％Ba(Cu 1/2 W 1/2 )O 3 +2.5mol％B 2 O 3 Batching, taking absolute ethyl alcohol as a medium, ball milling for 24 hours, taking out, drying and sieving with 200 meshes for standby;
(4) Placing the powder synthesized in the step (3) into a hot-pressing sintering machine, adopting an alumina corundum mold, directly heating to 100 ℃ at a heating rate of 5 ℃/min under the air or pure oxygen atmosphere condition, preserving heat for 15min to remove water vapor in the powder, heating to a sintering temperature of 880 ℃ at a heating rate of 20 ℃/min, preserving heat, gradually pressurizing to 25Mpa, preserving heat and pressure for 30min, powering off, cooling with boiled water, and rapidly cooling to room temperature;
(5) Cutting the sintered sample into ceramic plates with different sizes according to the requirements, polishing and processing the ceramic plates into thin plates with smooth two sides and thickness of 1.0mm, wherein the thin plates are in a coin shape or a cuboid shape and are coated with silver electrodes;
(6) Polarizing the fired piezoelectric ceramic sheet in silicone oil, polarizing the electric field at 6000V/mm, maintaining the temperature at 120 ℃ for 30min, maintaining the electric field and cooling to room temperature.
5. The bismuth ferrite-barium titanate ceramic having high curie temperature and high piezoelectric properties according to claim 1, wherein the ceramic has a chemical formula of:
0.70BiFeO 3 -0.30BaTiO 3 +1.0mol％MnCO 3 +2.0mol％Ba(Cu 1/2 W 1/2 )O 3 +2.5mol％B 2 O 3 +1.5mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 。
6. the bismuth ferrite-barium titanate ceramic having high curie temperature and high piezoelectric properties according to claim 1, wherein the ceramic has a chemical formula of:
0.65BiFeO 3 -0.35BaTiO 3 +1.0mol％MnCO 3 +1.0mol％Ba(Cu 1/2 W 1/2 )O 3 +2.5mol％B 2 O 3 +1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 。
7. the bismuth ferrite-barium titanate ceramic having high curie temperature and high piezoelectric properties according to claim 1, wherein the ceramic has a chemical formula of:
0.75BiFeO 3 -0.25BaTiO 3 +1.0mol％MnCO 3 +2.0mol％Ba(Cu 1/2 W 1/2 )O 3 +1.0mol％B 2 O 3 +1.0mol％(Bi 0.5 Na 0.25 Li 0.25 )TiO 3 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210912495.XA CN115073159B (en) | 2022-07-30 | 2022-07-30 | Bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance and low-temperature oxygen-containing hot pressed sintering preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210912495.XA CN115073159B (en) | 2022-07-30 | 2022-07-30 | Bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance and low-temperature oxygen-containing hot pressed sintering preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115073159A CN115073159A (en) | 2022-09-20 |
| CN115073159B true CN115073159B (en) | 2023-09-26 |
Family
ID=83242407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210912495.XA Active CN115073159B (en) | 2022-07-30 | 2022-07-30 | Bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance and low-temperature oxygen-containing hot pressed sintering preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115073159B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541978A (en) * | 2003-11-07 | 2004-11-03 | 四川大学 | Bismuth sodium lithium titanate barium titanate strontium titanate calcium titanate based lead-free piezoelectric ceramics |
| JP2007031219A (en) * | 2005-07-28 | 2007-02-08 | Toyota Motor Corp | Bismuth sodium titanate-barium zirconium titanate base lead-free piezoelectric ceramic and its producing method |
| WO2008078703A1 (en) * | 2006-12-25 | 2008-07-03 | Kyocera Corporation | Piezoelectric ceramic and piezoelectric element |
| CN104387049A (en) * | 2014-11-27 | 2015-03-04 | 桂林电子科技大学 | Leadless piezoelectric ceramic and method for preparing leadless piezoelectric ceramic by virtue of low-temperature liquid phase sintering |
| JP2015130505A (en) * | 2013-06-28 | 2015-07-16 | セイコーエプソン株式会社 | Method for manufacturing piezoelectric material, piezoelectric element, liquid ejecting head, liquid ejecting apparatus, ultrasonic sensor, piezoelectric motor, and power generator |
| CN110128127A (en) * | 2019-07-01 | 2019-08-16 | 桂林电子科技大学 | A kind of bismuth ferrite with high tension performance and high-temperature stability-barium titanate-based lead-free piezoelectric ceramics and preparation method thereof |
| CN110128126A (en) * | 2019-07-01 | 2019-08-16 | 桂林电子科技大学 | A kind of bismuth ferrite-metatitanic acid barium-zinc bismuth titanates-bismuth aluminate high-temp leadless piezoelectric ceramics and preparation method thereof |
| CN110128128A (en) * | 2019-07-01 | 2019-08-16 | 桂林电子科技大学 | A kind of bismuth ferrite-bismuth aluminate with zero-temperature coefficient and high-temperature stability-zinc bismuth titanates high-temperature piezoelectric ceramics and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7959823B2 (en) * | 2005-10-27 | 2011-06-14 | Kyocera Corporation | Piezoelectric ceramic composition and piezoelectric ceramic |
-
2022
- 2022-07-30 CN CN202210912495.XA patent/CN115073159B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541978A (en) * | 2003-11-07 | 2004-11-03 | 四川大学 | Bismuth sodium lithium titanate barium titanate strontium titanate calcium titanate based lead-free piezoelectric ceramics |
| JP2007031219A (en) * | 2005-07-28 | 2007-02-08 | Toyota Motor Corp | Bismuth sodium titanate-barium zirconium titanate base lead-free piezoelectric ceramic and its producing method |
| WO2008078703A1 (en) * | 2006-12-25 | 2008-07-03 | Kyocera Corporation | Piezoelectric ceramic and piezoelectric element |
| JP2015130505A (en) * | 2013-06-28 | 2015-07-16 | セイコーエプソン株式会社 | Method for manufacturing piezoelectric material, piezoelectric element, liquid ejecting head, liquid ejecting apparatus, ultrasonic sensor, piezoelectric motor, and power generator |
| CN104387049A (en) * | 2014-11-27 | 2015-03-04 | 桂林电子科技大学 | Leadless piezoelectric ceramic and method for preparing leadless piezoelectric ceramic by virtue of low-temperature liquid phase sintering |
| CN110128127A (en) * | 2019-07-01 | 2019-08-16 | 桂林电子科技大学 | A kind of bismuth ferrite with high tension performance and high-temperature stability-barium titanate-based lead-free piezoelectric ceramics and preparation method thereof |
| CN110128126A (en) * | 2019-07-01 | 2019-08-16 | 桂林电子科技大学 | A kind of bismuth ferrite-metatitanic acid barium-zinc bismuth titanates-bismuth aluminate high-temp leadless piezoelectric ceramics and preparation method thereof |
| CN110128128A (en) * | 2019-07-01 | 2019-08-16 | 桂林电子科技大学 | A kind of bismuth ferrite-bismuth aluminate with zero-temperature coefficient and high-temperature stability-zinc bismuth titanates high-temperature piezoelectric ceramics and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Ying Li 等."Enhancement in multiferroic and piezoelectric properties of BiFeO3–BaTiO3–Bi0.5Na0.5TiO3 lead-free ceramics with MnO2 addition by optimizing sintering temperature and dwell time".《Materials Research Bulletin》.2015,第92-99页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115073159A (en) | 2022-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110272270B (en) | Bismuth ferrite-barium titanate-based high-temperature lead-free piezoelectric ceramic with low dielectric loss and high-temperature stability and preparation method thereof | |
| CN109354492B (en) | Bismuth-based lead-free high-energy-density ceramic material and preparation method thereof | |
| JP5114730B2 (en) | Method for manufacturing piezoelectric ceramics | |
| CN107698252B (en) | Application of ceramic material as high-temperature stable piezoelectric energy collecting material and preparation method thereof | |
| CN108546125B (en) | Piezoceramic material applied to high-temperature environment and preparation method thereof | |
| CN110128127B (en) | Bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic with high piezoelectric performance and high-temperature stability and preparation method thereof | |
| CN114621004B (en) | High-entropy ceramic material with high energy storage density and preparation method thereof | |
| CN109553413B (en) | Textured piezoelectric ceramic and preparation method and application thereof | |
| CN111747740B (en) | Samarium ion doped lead zirconate titanate based high-performance piezoelectric ceramic and preparation method thereof | |
| CN111233465A (en) | Sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic and preparation method thereof | |
| CN113213929A (en) | Potassium sodium niobate based ferroelectric ceramic material with high energy storage efficiency and density and preparation method thereof | |
| CN109320244B (en) | Low-temperature sintered piezoelectric ceramic material and preparation method thereof | |
| CN107903055B (en) | Gradient doped sodium bismuth titanate based multilayer lead-free piezoelectric ceramic | |
| CN111072065A (en) | (111) oriented strontium titanate template material and preparation method thereof | |
| CN113979748A (en) | Potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method thereof | |
| CN103880416B (en) | Preparation method for sintering sodium bismuth titanate-based lead-free piezoelectric ceramics at low temperature | |
| CN115073159B (en) | Bismuth ferrite-barium titanate ceramic with high Curie temperature and high piezoelectric performance and low-temperature oxygen-containing hot pressed sintering preparation method thereof | |
| CN112457011A (en) | Quaternary piezoelectric ceramic for loudspeaker and preparation method thereof | |
| CN107021754B (en) | Dispersant modified relaxation type niobium nickel zirconium lead titanate piezoelectric ceramic and preparation method thereof | |
| CN109456055A (en) | A kind of high breakdown high polarization bismuth-sodium titanate ceramic material, preparation method and application | |
| CN115073160B (en) | Hot-pressed sintering preparation method of bismuth ferrite-barium titanate ceramic with micro-nano electric domain structure | |
| CN115321980A (en) | Preparation method of potassium-sodium niobate (KNN) based lead-free piezoelectric ceramic | |
| CN115093212B (en) | High-performance bismuth ferrite-barium titanate ceramic with use temperature exceeding 300 ℃ and low-temperature liquid phase sintering preparation method thereof | |
| CN103159475B (en) | Leadless piezoelectric ceramic composed of B-bit composite Bi-based compound and preparation method thereof | |
| CN116768626B (en) | PbNb (PbNb) material 2 O 6 Base piezoelectric ceramic material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |