CN109279891B - Bismuth ferrite based electrostrictive strain ceramic and preparation method and application thereof - Google Patents

Bismuth ferrite based electrostrictive strain ceramic and preparation method and application thereof Download PDF

Info

Publication number
CN109279891B
CN109279891B CN201811145258.5A CN201811145258A CN109279891B CN 109279891 B CN109279891 B CN 109279891B CN 201811145258 A CN201811145258 A CN 201811145258A CN 109279891 B CN109279891 B CN 109279891B
Authority
CN
China
Prior art keywords
ceramic
bismuth ferrite
temperature
zro
ball milling
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
Application number
CN201811145258.5A
Other languages
Chinese (zh)
Other versions
CN109279891A (en
Inventor
翟继卫
刘星
沈波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tongji University
Original Assignee
Tongji University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tongji University filed Critical Tongji University
Priority to CN201811145258.5A priority Critical patent/CN109279891B/en
Publication of CN109279891A publication Critical patent/CN109279891A/en
Application granted granted Critical
Publication of CN109279891B publication Critical patent/CN109279891B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C04B35/453—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 zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C04B35/62615—High energy or reactive ball milling
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62695—Granulation or pelletising
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
    • G01B7/02—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring length, width or thickness
    • 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
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3248—Zirconates or hafnates, e.g. zircon
    • 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • 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
    • C04B2235/70—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)

Abstract

The invention relates to bismuth ferrite-based electrostrictive strain ceramic and a preparation method and application thereof, wherein the ceramic comprises (0.67-x) Bi1.02FeO3‑0.33BaTiO3‑x(Ba0.8Ca0.2)ZrO3And x is 0-0.06, and the preparation method adopts a solid-phase sintering method, and comprises the steps of mixing the raw materials according to a formula, carrying out primary ball milling and calcining at 800-900 ℃ to obtain pre-synthesized precursor powder. And performing secondary ball milling, drying granulation and compression molding to obtain a ceramic green body, and performing high-temperature sintering at 950-1100 ℃ after removing the gel to obtain a compact high-performance bismuth ferrite-based ceramic sample. Compared with the traditional lead-based electrostrictive strain material, the lead-based electrostrictive strain material has the most obvious advantages of environment-friendly material, high dynamic piezoelectric coefficient, low strain hysteresis and excellent high-temperature stability, and can be widely used for manufacturing drivers and high-precision displacement sensors.

Description

Bismuth ferrite based electrostrictive strain ceramic and preparation method and application thereof
Technical Field
The invention relates to the field of driver ceramic materials, in particular to bismuth ferrite-based electrostrictive strain ceramic and a preparation method and application thereof.
Background
The electrostriction is a direct embodiment of the inverse piezoelectric effect of piezoelectric materials, and is mainly applied to drivers and displacement sensors, wherein the dynamic piezoelectric coefficient (d)33 *) Is a main index for evaluating the driver material. Traditional lead-based lead zirconate titanate (PZT) ceramics are widely used due to high piezoelectric property, high strain and excellent temperature stability, however, PZT and modified ceramics thereof contain a large amount of toxic lead oxide, which not only can cause great damage to the environment but also to the human body, so a high-performance lead-free ceramic system must be explored to replace lead-based materials. In recent years, bismuth-based lead-free perovskite materials have been extensively studied, among which sodium bismuth titanate (Bi)0.5Na0.5TiO3BNT) has high electrostriction and no hysteresisCan, this property is achieved mainly by incorporation of other elements or ABO3The perovskite composite material reduces the ferroelectric-relaxor phase transition temperature to below room temperature. However, although the BNT-based ceramic has a high strain output of 0.3-0.5%, the strain hysteresis is as high as 60-70%, and such a large hysteresis greatly reduces the detection accuracy of the actuator or the displacer, which is not favorable for practical applications. Meanwhile, the temperature stability of the BNT-based material is low, and the performance of the BNT-based material is only 50% of that of the BNT-based material at room temperature after the BNT-based material is heated to 100 ℃. Therefore, there is a need to develop new high performance, low hysteresis lead-free electrostrictive ceramics to replace lead-based materials.
Bismuth ferrite (BiFeO)3) The lead-free perovskite-based material has ultrahigh Curie temperature (T)c830 ℃ C.) and ferroelectric polarization (P)r～100μC/cm2) And the method has wide application prospect in the fields of high-temperature piezoelectricity and novel ferroelectric devices. However, pure bismuth ferrite ceramics are easy to form secondary phases during high-temperature sintering, and the sintering temperature zone is too narrow to prepare. The leakage of the bismuth ferrite ceramic can be reduced to a certain extent by a rapid quenching process, but the process is easy to cause large internal stress to crack the ceramic, and is not beneficial to practical application. A series of researches show that bismuth ferrite and other ABOs are mixed3The perovskite material is compounded to effectively reduce the leakage current of the system, wherein BiFeO3-BaTiO3The system has relatively high residual polarization and Curie temperature, presents a morphotropic phase boundary when x is 0.33, but has low electrostrictive performance (0.1-0.2%), and cannot meet the requirements of practical application. At present, few reports are provided for bismuth ferrite-based high electrostrictive ceramics.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a bismuth ferrite-based ceramic with low hysteresis, stable temperature and high electrostrictive strain.
The invention also aims to provide a preparation method of the bismuth ferrite-based electrostrictive ceramic.
Another object of the present invention is to provide the use of bismuth ferrite based electrostrictive ceramics.
The purpose of the invention can be realized by the following technical scheme:
the bismuth ferrite-based electrostrictive strain ceramic has the chemical composition of (0.67-x) Bi1.02FeO3-0.33BaTiO3-x(Ba0.8Ca0.2)ZrO3Wherein x is 0 to 0.06, and preferably x is 0.02.
The preparation method of the bismuth ferrite-based electrostrictive strain ceramic uses a solid phase reaction method to prepare a ceramic material, and specifically comprises the following steps:
(1) selecting Bi with the purity of more than 99 percent2O3、Fe2O3、BaCO3、TiO2、CaCO3And ZrO2As a raw material for preparing bismuth ferrite-based ceramics;
(2) according to (0.67-x) Bi1.02FeO3-0.33BaTiO3-x(Ba0.8Ca0.2)ZrO3Weighing raw materials according to the chemical proportion of x being 0-0.06, performing primary ball milling, and drying to obtain precursor powder;
(3) calcining the precursor powder at the temperature of 800-900 ℃ for 2-6h to obtain pre-synthesized powder;
(4) performing secondary ball milling, drying and granulation on the pre-synthesized powder, pressing the pre-synthesized powder into a ceramic blank under the pressure of 60-100MPa, performing glue removal treatment at the temperature of 500-600 ℃, and preserving heat for 6-12 h;
(5) and sintering the blank after the glue is removed at 950-1100 ℃ for 2-6h, and cooling to room temperature along with the furnace to obtain the sodium bismuth titanate based electrostrictive ceramic.
The step (2) and the step (4) adopt absolute ethyl alcohol and ZrO during ball milling2The balls being as a ball-milling medium, ZrO2The mass ratio of the balls to the ball grinding materials is 1.1-1.4: 1, and the mass ratio of the absolute ethyl alcohol to the raw materials is 1.1-2.4: 1.
Setting ball milling parameters of the step (2) and the step (4) as follows: the ball milling rotation speed is 280 plus 400r/min, and the ball milling time is 10-20 h.
And (4) when the powder material in the step (4) is granulated, 5wt% of PVA is used, and the size of the ceramic blank obtained by pressing is 10-12 mm in diameter and 0.8-1 mm in thickness.
The sintering temperature adopted in the step (5) is preferably 1000 ℃, and the heat preservation time is preferably 3 h.
The bismuth ferrite-based ceramic has low hysteresis and high electrostrictive strain performance, is beneficial to controlling the change of displacement with extremely small size in the aspects of a driver and a displacement sensor, has the characteristics of quick response time, high temperature stability and the like, and has extremely high practical application value.
The invention is innovatively in BiFeO3-BaTiO3Incorporation of (Ba) into ceramics0.8Ca0.2)ZrO3Constructed (0.67-x) Bi1.02FeO3-0.33BaTiO3-x(Ba0.8Ca0.2)ZrO3The novel ternary system ceramic has a special high-activity relaxation phase structure near room temperature, and the potential barrier difference between the relaxation phase and a ferroelectric phase is small, so that hysteresis generated in the field-induced phase change process is greatly reduced, and the improvement of the precision of a driver is facilitated. In addition, the high-activity relaxation phase of the ternary system ceramic has higher stability, can realize effective conversion with a ferroelectric phase in a wider temperature zone range, and improves the temperature stability of the electrostrictive strain performance, so that the bismuth ferrite-based ceramic system is a novel lead-free material with wide application prospect in a driver and a sensor.
Compared with the prior art, the invention constructs the novel ternary system bismuth ferrite-based lead-free ceramic (0.67-x) Bi1.02FeO3-0.33BaTiO3-x(Ba0.8Ca0.2)ZrO3. Particularly, when x is 0.02, the dynamic piezoelectric coefficient of the piezoelectric actuator can be as high as 640pm/V, which is obviously higher than that of bismuth ferrite ceramics reported in other documents, and the corresponding strain hysteresis is only 33%, which is reduced by half compared with BNT-based electrostriction ceramics, thereby greatly improving the detection precision of the actuator. Meanwhile, the electrostrictive strain performance can be kept stable in a wider temperature range from room temperature to 120 ℃, and excellent temperature stability is reflected. The bismuth ferrite-based electrostrictive strain ceramic prepared by the invention can be applied to drivers and high-precision displacement controllers, and the discovery of bismuth ferrite-based materials has great significance for replacing lead-based electrostrictive strain materials.
Drawings
FIG. 1 is a dielectric temperature spectrum at 1kHz of bismuth ferrite-based electrostrictive ceramics prepared in examples 1 to 4;
FIG. 2 is a unidirectional electrical strain curve of the bismuth ferrite based electrical strain ceramic prepared in examples 1-4
FIG. 3 is the electric strain curve of the bismuth ferrite-based electric strain ceramic prepared in example 2 at different temperatures;
FIG. 4 shows the dynamic d of the bismuth ferrite based electrostrictive ceramics obtained in example 233 *The coefficient and strain hysteresis vary with temperature.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The bismuth ferrite-based lead-free ceramic has the chemical composition of (0.67-x) Bi1.02FeO3-0.33BaTiO3-x(Ba0.8Ca0.2)ZrO3Wherein x is 0, the preparation method comprises the following steps:
(1) selecting Bi with the purity of more than 99 percent2O3、Fe2O3、BaCO3、TiO2、CaCO3And ZrO2As the raw material of bismuth ferrite-based electrostrictive strain ceramic;
(2) according to 0.67Bi1.02FeO3-0.33BaTiO3The formula of the material is weighed, and is dried after primary ball milling, and absolute ethyl alcohol and ZrO are adopted during ball milling2The balls being as a ball-milling medium, ZrO2The mass ratio of the balls to the raw materials is 1.3:1, the mass ratio of the absolute ethyl alcohol to the raw materials is 1.5:1, the ball milling rotation speed is 280r/min, and the ball milling time is 10 hours;
(3) presintering the dried precursor powder at 800 ℃ for 4h to obtain calcined powder;
(4) performing secondary ball milling on the calcined powder by adoptingAnhydrous ethanol and ZrO2The balls being as a ball-milling medium, ZrO2The mass ratio of the balls to the raw materials is 1.3:1, the mass ratio of the absolute ethyl alcohol to the raw materials is 1.5:1, the ball milling rotation speed is 280r/min, and the ball milling time is 10 hours. Then drying, adding 5wt% of PVA for granulation, pressing into a ceramic blank with the diameter of 10mm and the thickness of 0.8mm under the pressure of 60MPa, and carrying out glue removal at 550 ℃ for 12 h;
(5) and sintering the blank after the glue is removed at 950 ℃ for 3h, wherein the temperature rise rate during sintering is 3 ℃/min, and thinning and polishing the sample to obtain the bismuth ferrite-based electrostrictive ceramics. The method can be applied to drivers and high-precision displacement sensors.
Example 2
The bismuth ferrite-based ceramic with high electric induced strain has a chemical composition of (0.67-x) Bi1.02FeO3-0.33BaTiO3-x(Ba0.8Ca0.2)ZrO3Wherein x is 0.02, and the preparation method comprises the following steps:
(1) selecting Bi with the purity of more than 99 percent2O3、Fe2O3、BaCO3、TiO2、CaCO3And ZrO2As the raw material of bismuth ferrite-based electrostrictive strain ceramic;
(2) according to 0.65Bi1.02FeO3-0.33BaTiO3-0.02(Ba0.8Ca0.2)ZrO3The formula of the material is weighed, and the material is dried after primary ball milling, wherein absolute ethyl alcohol and ZrO are adopted during ball milling2The balls being as a ball-milling medium, ZrO2The mass ratio of the balls to the raw materials is 1.4:1, the mass ratio of the absolute ethyl alcohol to the raw materials is 1.7:1, the ball milling speed is 300r/min, and the ball milling time is 12 hours;
(3) presintering the dried precursor powder for 4h at 800 ℃;
(4) carrying out secondary ball milling on the calcined powder, wherein absolute ethyl alcohol and ZrO are adopted during ball milling2The balls being as a ball-milling medium, ZrO2The mass ratio of the balls to the raw materials is 1.4:1, the mass ratio of the absolute ethyl alcohol to the raw materials is 1.7:1, the ball milling rotation speed is 300r/min, the ball milling time is 12 hours, then 5wt% of PVA is added into the dried materials for granulation, and the granulation is carried out under the pressure of 80MPaPressing into a ceramic blank with the diameter of 10mm and the thickness of 0.9mm, carrying out glue discharging at 550 ℃, and carrying out heat preservation for 10 hours;
(5) and (3) sintering the blank at the high temperature of 1000 ℃ for 4h at the heating rate of 3 ℃/min, cooling the blank to room temperature along with the furnace, and then thinning and polishing the ceramic to obtain the bismuth ferrite-based electrostrictive ceramic sample. The ceramic can be applied to a driver and a high-precision displacement sensor.
Example 3
The bismuth ferrite-based electrostrictive strain ceramic comprises (0.67-x) Bi1.02FeO3-0.33BaTiO3-x(Ba0.8Ca0.2)ZrO3Wherein x is 0.04, and the preparation method comprises the following steps:
(1) selecting Bi with the purity of more than 99 percent2O3、Fe2O3、BaCO3、TiO2、CaCO3And ZrO2As the raw material of bismuth ferrite-based electrostrictive strain ceramic;
(2) according to 0.63Bi1.02FeO3-0.33BaTiO3-0.04(Ba0.8Ca0.2)ZrO3The raw materials are weighed according to the formula, are dried after ball milling, and absolute ethyl alcohol and ZrO are adopted during ball milling2The balls being as a ball-milling medium, ZrO2The mass ratio of the balls to the raw materials is 1.4:1, the mass ratio of the absolute ethyl alcohol to the raw materials is 2:1, the ball milling speed is controlled at 350r/min, and the ball milling time is 15 hours;
(3) preburning the dried raw materials at 875 ℃ for 3 h;
(4) performing secondary ball milling on the pre-sintered powder, wherein absolute ethyl alcohol and ZrO are adopted during ball milling2The balls being as a ball-milling medium, ZrO2The mass ratio of the balls to the raw materials is 1.4:1, the mass ratio of the absolute ethyl alcohol to the raw materials is 2.5:1, the ball milling speed is controlled at 350r/min, and the ball milling time is 15 hours. Adding 5wt% of PVA into the dried material for granulation, pressing the mixture into a ceramic blank body with the diameter of 10mm and the thickness of 1mm under the pressure of 100MPa, and carrying out glue discharging at the temperature of 600 ℃, wherein the heating rate is 1 ℃/min and the heat preservation time is 8 h;
(5) and sintering the blank after the glue is removed at 1050 ℃ for 5h, controlling the heating rate to be 3 ℃/min during sintering, naturally cooling to room temperature, and thinning and polishing a sintered ceramic sample to obtain the bismuth ferrite-based electrostrictive ceramic. The ceramic can be applied to a driver and a high-precision displacement sensor.
Example 4
The bismuth ferrite-based electrostrictive strain ceramic comprises 0.61Bi as a raw material1.02FeO3-0.33BaTiO3-0.06(Ba0.8Ca0.2)ZrO3Wherein x is 0.06, the preparation method comprises the following steps:
(1) selecting Bi with the purity of more than 99 percent2O3、Fe2O3、BaCO3、TiO2、CaCO3And ZrO2As a raw material of bismuth ferrite-based ceramics;
(2) according to 0.61Bi1.02FeO3-0.33BaTiO3-0.06(Ba0.8Ca0.2)ZrO3The raw materials are weighed according to the formula, are dried after ball milling, and absolute ethyl alcohol and ZrO are adopted during ball milling2The balls being as a ball-milling medium, ZrO2The mass ratio of the balls to the raw materials is 1.4:1, the mass ratio of the absolute ethyl alcohol to the raw materials is 2.4:1, the ball milling speed is controlled at 400r/min, and the ball milling time is 20 hours;
(3) calcining the dried raw materials at 900 ℃ for 5 hours;
(4) carrying out secondary ball milling on the calcined powder, wherein absolute ethyl alcohol and ZrO are adopted during ball milling2The balls being as a ball-milling medium, ZrO2The mass ratio of the balls to the raw materials is 1.4:1, the mass ratio of the absolute ethyl alcohol to the raw materials is 2.4:1, the ball milling rotating speed is controlled at 400r/min, and the ball milling time is 20 hours. Then drying and granulating, adding 5wt% of PVA before granulating, pressing into a ceramic blank with the diameter of 10mm and the thickness of 1mm under the pressure of 100MPa, carrying out glue discharging at the temperature of 600 ℃, and keeping the temperature for 5 hours;
(5) and sintering the green body after the glue is removed at 1100 ℃ for 5h, controlling the heating rate to be 3 ℃/min during sintering, cooling to room temperature along with the furnace, thinning and polishing the sample to obtain the bismuth ferrite-based electrostrictive ceramic. The ceramic can be applied to a driver and a high-precision displacement sensor.
FIG. 1 is a dielectric temperature spectrum of bismuth ferrite-based electrostrictive strain ceramic prepared by the invention under 1kHz, wherein the dielectric temperature peak of the component x ═ 0 is sharper, and the Curie temperature is 425 ℃. As the content of x increases, the mesophilic peak gradually shifts to a low temperature region, and the curie temperature of x ═ 0.02 component is 360 ℃. And simultaneously, the medium temperature peak gradually widens and disperses, and the characteristics of the relaxor ferroelectric are presented.
FIG. 2 is a unidirectional electrostrictive strain curve of the bismuth ferrite based electrostrictive strain ceramic prepared by the present invention. The ceramic prepared in example 2, i.e. the x ═ 0.02 component, had the highest electrostrictive properties, corresponding to a dynamic d33 *The coefficient reached 640pm/V and the strain hysteresis was 33%. The low hysteresis high electrical strain performance is related to the traversing relaxation phase structure of the x ═ 0.02 component at room temperature, and mainly results from field reversible traversing relaxation to ferroelectric phase transition.
FIG. 3 is a schematic diagram of the electrical strain of the bismuth ferrite-based electrically strained ceramic prepared in example 2 of the present invention at different temperatures, and the testing electric field is 6 kV/mm. As the temperature increases, the strain hysteresis decreases substantially, while the unidirectional strain value increases gradually.
FIG. 4 is the dynamic piezoelectric d of the bismuth ferrite based electrostrictive ceramics obtained in example 233 *The coefficient and hysteresis vary with temperature. With increasing temperature, d33 *The coefficient gradually increases and the hysteresis decreases substantially. At 120 ℃, the dynamic piezoelectric coefficient reaches 717pm/V, and the hysteresis is reduced to 13%, which shows that the bismuth ferrite-based electrostrictive strain ceramic prepared by the invention has excellent high-temperature electrostrictive strain performance and is expected to replace the traditional lead-based electrostrictive strain material.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (7)

1. The bismuth ferrite based electrostrictive strain ceramic is characterized in that the chemical composition of the ceramic is (0.67-x) Bi1.02FeO3-0.33BaTiO3-x(Ba0.8Ca0.2)ZrO3Wherein x =0.02,
the preparation method comprises the following steps:
(1) with Bi2O3、Fe2O3、BaCO3、TiO2、CaCO3And ZrO2As a raw material of bismuth ferrite-based ceramics;
(2) according to (0.67-x) Bi1.02FeO3-0.33BaTiO3-x(Ba0.8Ca0.2)ZrO3Weighing the raw materials according to the chemical formula, and performing primary ball milling to obtain raw material precursor powder;
(3) calcining the precursor powder at the temperature of 800-900 ℃ for 2-5h to obtain pre-synthesized powder;
(4) carrying out secondary ball milling on the calcined powder, and granulating and carrying out compression molding on the dried powder to obtain a ceramic blank;
(5) removing colloidal organic matters from the ceramic blank at the temperature of 500-600 ℃, keeping the temperature for 5-12h, carrying out high-temperature sintering after removing the gel, wherein the sintering temperature is 950-1100 ℃, the heating rate is 2-6 ℃/min, the keeping temperature for 2-5h, and cooling to room temperature along with a furnace to obtain the bismuth ferrite-based electrostrictive ceramic;
the step (2) and the step (4) adopt absolute ethyl alcohol and ZrO during ball milling2The balls being as a ball-milling medium, ZrO2The mass ratio of the balls to the ball grinding materials is 1.1-1.4: 1, and the mass ratio of the absolute ethyl alcohol to the raw materials is 1.1-2.4: 1.
2. The preparation method of the bismuth ferrite based electrostrictive ceramic as claimed in claim 1, wherein the method comprises the following steps:
(1) with Bi2O3、Fe2O3、BaCO3、TiO2、CaCO3And ZrO2As a raw material of bismuth ferrite-based ceramics;
(2) according to (0.67-x) Bi1.02FeO3-0.33BaTiO3-x(Ba0.8Ca0.2)ZrO3Weighing the raw materials according to the chemical formula, and performing primary ball milling to obtain raw material precursor powder;
(3) calcining the precursor powder at the temperature of 800-900 ℃ for 2-5h to obtain pre-synthesized powder;
(4) carrying out secondary ball milling on the calcined powder, and granulating and carrying out compression molding on the dried powder to obtain a ceramic blank;
(5) removing colloidal organic matters from the ceramic blank at the temperature of 500-600 ℃, keeping the temperature for 5-12h, carrying out high-temperature sintering after removing the gel, wherein the sintering temperature is 950-1100 ℃, the heating rate is 2-6 ℃/min, the keeping temperature for 2-5h, and cooling to room temperature along with a furnace to obtain the bismuth ferrite-based electrostrictive ceramic;
the step (2) and the step (4) adopt absolute ethyl alcohol and ZrO during ball milling2The balls being as a ball-milling medium, ZrO2The mass ratio of the balls to the ball grinding materials is 1.1-1.4: 1, and the mass ratio of the absolute ethyl alcohol to the raw materials is 1.1-2.4: 1.
3. The method for preparing bismuth ferrite based electrostrictive strain ceramic as claimed in claim 2, wherein the rotation speed of ball milling in steps (2) and (4) is controlled to be 280-400r/min during ball milling, and the time is 10-20 h.
4. The method for preparing bismuth ferrite based electrostrictive ceramics according to claim 2, wherein PVA is added to the powder in the step (4) during the granulation process, and the addition amount is 5wt% of the powder.
5. The method for preparing the bismuth ferrite based electrostrictive ceramic as claimed in claim 2, wherein the molding pressure during the compression molding of the ceramic green body in the step (4) is 60 to 100 MPa.
6. The method for preparing the bismuth ferrite based electrostrictive ceramic as claimed in claim 2, wherein the sintering temperature in step (5) is 1000 ℃, and the holding time is 3 hours.
7. The use of the bismuth ferrite-based electrostrictive ceramic of claim 1 in the manufacture of actuators and high precision displacement sensors.
CN201811145258.5A 2018-09-29 2018-09-29 Bismuth ferrite based electrostrictive strain ceramic and preparation method and application thereof Active CN109279891B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811145258.5A CN109279891B (en) 2018-09-29 2018-09-29 Bismuth ferrite based electrostrictive strain ceramic and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811145258.5A CN109279891B (en) 2018-09-29 2018-09-29 Bismuth ferrite based electrostrictive strain ceramic and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109279891A CN109279891A (en) 2019-01-29
CN109279891B true CN109279891B (en) 2022-02-18

Family

ID=65182130

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811145258.5A Active CN109279891B (en) 2018-09-29 2018-09-29 Bismuth ferrite based electrostrictive strain ceramic and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109279891B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062551A (en) * 2020-08-06 2020-12-11 同济大学 Bismuth ferrite-based piezoelectric ceramic material with high depolarization temperature and high piezoelectric performance and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106977196A (en) * 2017-03-24 2017-07-25 同济大学 A kind of non-stoichiometric bismuth-sodium titanate base ceramics and its preparation method and application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106977196A (en) * 2017-03-24 2017-07-25 同济大学 A kind of non-stoichiometric bismuth-sodium titanate base ceramics and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A Novel BiFeO3–BaTiO3–BaZrO3 Lead-Free Relaxor Ferroelectric Ceramic with Low-Hysteresis and Frequency-Insensitive Large Strains;Zheng Donggeng等;《Journal of the American Ceramic Society》;20150918;第98卷(第12期);第3670-3672页 *
Lead-free Bi1/2(Na0.82K0.18)1/2TiO3 ceramics exhibiting large strain with small hysteresis;Lee H B等;《Ceramics International》;20130530;第39卷(第1期);第1-4页 *

Also Published As

Publication number Publication date
CN109279891A (en) 2019-01-29

Similar Documents

Publication Publication Date Title
CN111302797B (en) Potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method thereof
CN109534810B (en) Sodium bismuth titanate-based lead-free driver ceramic and preparation method and application thereof
CN108147813B (en) Sodium bismuth titanate-based lead-free piezoelectric ceramic with high piezoelectric coefficient and preparation method thereof
CN109796205B (en) Bismuth-layer-structured bismuth titanium tantalate high-temperature piezoelectric ceramic material and preparation method thereof
CN111072385A (en) Calcium zirconate and tantalum doped potassium sodium niobate based piezoelectric ceramic, and preparation method and application thereof
CN113582667B (en) Low-temperature cofiring high-energy-storage antiferroelectric ceramic material and preparation method and application thereof
CN112062551A (en) Bismuth ferrite-based piezoelectric ceramic material with high depolarization temperature and high piezoelectric performance and preparation method thereof
CN116573936B (en) Anion modified piezoelectric ceramic and preparation method thereof
CN110550953A (en) Sodium bismuth titanate-based lead-free piezoelectric ceramic and preparation method thereof
CN106977196B (en) Non-stoichiometric bismuth sodium titanate-based ceramic and preparation method and application thereof
CN112552048B (en) Preparation method of potassium-sodium niobate ceramic with high piezoelectric property and high remanent polarization
CN107903055B (en) Gradient doped sodium bismuth titanate based multilayer lead-free piezoelectric ceramic
CN109279891B (en) Bismuth ferrite based electrostrictive strain ceramic and preparation method and application thereof
CN107056290B (en) Method for regulating Curie temperature of ferroelectric ceramic
CN103482973A (en) Lead-free quaternary system electro-strain piezoelectric ceramic material, preparation method and product
CN107162585A (en) A kind of bismuth-sodium titanate base electrostriction ceramics and its preparation method and application
CN115385675B (en) Bismuth ferrite based lead-free ferroelectric ceramic material with high Curie temperature and energy storage characteristic and preparation method thereof
CN102432285B (en) Bismuth titanium-nickel-bismuth titanium-zinc-lead titanate ternary system high temperature piezoelectric ceramics and preparation method thereof
CN111217596B (en) Lead-free piezoelectric ceramic material with high Curie temperature and large electrostrictive strain and preparation method thereof
CN112062559B (en) Antiferroelectric ceramic material and low-temperature sintering method thereof
CN114478007A (en) Sodium niobate-based ceramic material with good process tolerance, high piezoelectric property and high dielectric property, and preparation method and application thereof
CN103539447B (en) Low-temperature sintered piezoelectric ceramic material and preparation method thereof
CN113248247A (en) Ternary piezoelectric ceramic and preparation method and application thereof
KR101806207B1 (en) Ternary lead-free piezoelectric ceramics with high strains and low temperature sintering and preparing method thereof
KR20180003277A (en) Producing method of lead-free piezoelectric ceramics with high strains

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