CN111592346B - High-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic and preparation method thereof - Google Patents

High-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic and preparation method thereof Download PDF

Info

Publication number
CN111592346B
CN111592346B CN202010421696.0A CN202010421696A CN111592346B CN 111592346 B CN111592346 B CN 111592346B CN 202010421696 A CN202010421696 A CN 202010421696A CN 111592346 B CN111592346 B CN 111592346B
Authority
CN
China
Prior art keywords
oxide
ceramic
meshes
mixture
purity
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
CN202010421696.0A
Other languages
Chinese (zh)
Other versions
CN111592346A (en
Inventor
柯华
田晶鑫
罗蕙佳代
曹璐
唐晓慧
邢苗
张洪军
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.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
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 Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN202010421696.0A priority Critical patent/CN111592346B/en
Publication of CN111592346A publication Critical patent/CN111592346A/en
Application granted granted Critical
Publication of CN111592346B publication Critical patent/CN111592346B/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
    • C04B35/26—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
    • C04B35/2675—Other ferrites containing rare earth metals, e.g. rare earth ferrite garnets
    • 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
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
    • 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
    • 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
    • C04B35/63—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 using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
    • 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
    • C04B35/63—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 using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/638—Removal 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
    • 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
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • 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
    • C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
    • 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
    • C04B2235/65—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
    • C04B2235/65—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
    • C04B2235/6565—Cooling 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
    • C04B2235/65—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
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
    • C04B2235/6585—Oxygen containing atmosphere, e.g. with changing oxygen pressures at an oxygen percentage above that of air
    • 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)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Magnetic Ceramics (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A high-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic and a preparation method thereof relate to a multi-ion co-doped bismuth ferrite-based ceramic with high ferroelectric property and a preparation method thereof. The invention aims to solve the problems of high ceramic leakage current and small ferroelectric polarization caused by poor purity and low densification degree of a bismuth ferrite ceramic phase synthesized by the existing method. The chemical general formula of the high-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic is as follows: bi1‑xRexFe1‑yByO3(ii) a The preparation method comprises the following steps: firstly, weighing materials; secondly, drying and sieving; thirdly, biscuit forming; and fourthly, sintering the ceramic. The bismuth ferrite-based ceramic prepared by the invention has high purity and density, and meanwhile, the leakage current is small, and the excellent ferroelectric property is shown. The invention can obtain the high-purity high-density bismuth ferrite-based ceramic.

Description

High-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic and preparation method thereof
Technical Field
The invention relates to a multi-ion co-doped bismuth ferrite-based ceramic with high ferroelectric property and a preparation method thereof.
Background
Bismuth ferrite (BiFeO)3) Currently, the single-phase multiferroic material at room temperature has attracted attention because of its ferroelectric and antiferromagnetic properties. Theoretical studies have shown that the Curie temperature Tc of bismuth ferrite is about 830 ℃ and the antiferromagnetic Neille temperature TNAbout 370 ℃ and spontaneous polarizationIs 100 mu C cm-2This makes it the preferred multiferroic material for applications at room temperature. The magnetic and electric mutual regulation and control effect in the multiferroic material has quite good application prospect in devices such as converters, oscillators, memories, particularly multi-state memories and the like.
However, the current research on bismuth ferrite still has certain difficulties, mainly including that the structure is unstable at high temperature, impure phases exist in the synthesis process, good ferroelectricity cannot be shown due to large leakage current, and the G-type antiferromagnetic structure of bismuth ferrite has weak magnetic performance and cannot show good magnetoelectric coupling effect at room temperature.
Disclosure of Invention
The invention aims to solve the problems that the bismuth ferrite ceramic synthesized by the existing method has poor phase purity and low densification degree, and further causes large ceramic leakage current and excessively small ferroelectric polarization, and provides a high-purity and high-densification A/B site multi-ion co-doped bismuth ferrite-based ceramic and a preparation method thereof.
The chemical general formula of the high-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic is as follows: bi1-xRexFe1- yByO3Wherein 0 is<x≤0.3，0<y is less than or equal to 0.1, x and y are mole fractions, Re is a rare earth element, and the rare earth element is one or a mixture of more of praseodymium element, neodymium element and samarium element; b is a high valence transition metal element, and the high valence transition metal element is one or a mixture of molybdenum, zirconium and titanium; bi is bismuth; the Fe is iron element.
A preparation method of high-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic is completed according to the following steps:
firstly, weighing materials:
firstly, Bi is according to a chemical general formula1-xRexFe1-yByO3Weighing bismuth oxide, ferric oxide, rare earth oxide and high-valence transition metal oxide powder; wherein 0<x≤0.3，0<y is less than or equal to 0.1, and x and y are mole fractions;
② weighing bismuth oxide again;
the molar ratio of the bismuth oxide weighed in the first step to the bismuth oxide weighed in the first step is (0.01-0.1): 1;
putting the powder of the bismuth oxide, the ferric oxide, the rare earth oxide and the transition metal oxide weighed in the first step and the first step into a ball milling tank, adding a ball milling medium, namely absolute ethyl alcohol and milling balls, and mixing the milling balls by using a high-energy planetary ball mill to obtain a mixture after ball milling;
secondly, drying the mixture subjected to ball milling, and sieving the dried mixture by using a 100-mesh sieve to obtain a raw material mixture with the particle size smaller than 100 meshes;
thirdly, biscuit forming:
firstly, adding a raw material mixture with the particle size of less than 100 meshes and a binder aqueous solution into an agate mortar for grinding and granulation, and then sieving the mixture through a sieve with 150 meshes to 200 meshes to obtain raw material mixed powder with the particle size of 150 meshes to 200 meshes;
the mass ratio of the raw material mixture with the particle size smaller than 100 meshes to the binder in the binder aqueous solution in the third step is (19-49): 1;
secondly, adding the raw material mixed powder with the particle size of 150-200 meshes into a round steel mould with the diameter of 10-30 mm, and maintaining the pressure at 400-700 MPa to obtain a compact blank;
thirdly, heating the compact blank to 200-300 ℃ at the heating rate of 1-2 ℃/min, heating to 500-550 ℃ at the heating rate of 0.5-1 ℃/min, preserving heat at 500-550 ℃ for 1-2 h, cooling to room temperature at the cooling rate of 5-10 ℃/min, and discharging the glue from the blank to obtain a blank after discharging the glue;
fourthly, sintering the ceramic:
firstly, heating the blank after the glue removal to 850-900 ℃ in an oxygen atmosphere, then preserving heat, then cooling to 770-870 ℃, preserving heat, and finally rapidly cooling to room temperature to obtain the high-purity and high-density A/B multi-ion co-doped bismuth ferrite-based ceramic.
Further, in the step one, the ball-material ratio is (10-15): 1, the ball-milling speed is 200 r/min-400 r/min, and the ball-milling time is 12 h-24 h;
further, the rare earth oxide in the first step is one or a mixture of praseodymium oxide, neodymium oxide and samarium oxide;
the high valence transition metal oxide powder in the first step is one or a mixture of molybdenum oxide, zirconium oxide and titanium oxide;
the aqueous solution of the binder in the third step is aqueous solution of polyvinyl alcohol; the mass ratio of polyvinyl alcohol to deionized water in the polyvinyl alcohol aqueous solution is (9-19) to 1;
drying the ball-milled mixture for 12 to 24 hours under vacuum pressure and constant temperature under the conditions that the vacuum degree is-0.05 to-0.08 MPa and the temperature is 60 to 80 ℃;
step three, the pressure maintaining time is 3-5 min;
in the fourth step, firstly, the blank after the glue discharging is heated to 850-900 ℃ at the heating rate of 10-30 ℃/min under the oxygen atmosphere, then the temperature is kept for 1-10 min, then the blank is cooled to 770-870 ℃ at the cooling rate of 10-30 ℃/min, and then the temperature is kept for 1-12 h;
and finally, in the fourth step, the mixture is rapidly cooled to room temperature at a cooling rate of 10-30 ℃/min.
The invention has the advantages that:
firstly, the invention adopts a proper synthesis process, introduces various ions into the bismuth ferrite ceramic, increases the entropy value, enriches the phase structure of the ceramic and is beneficial to the stability of the material;
the invention adopts a high-energy planetary ball milling mixing method when the raw material powder is mixed, which not only ensures that the raw material powder is fully and uniformly mixed, but also can refine the powder size, increase the powder activity and be beneficial to ceramic sintering, and adopts a vacuum reduced pressure drying method when the powder is dried, thereby providing a negative pressure drying environment and ensuring the rapid drying of the raw material mixture;
the granulation process is adopted during the green body forming, the granulated powder has uniform particle size and better fluidity, the compactness of the green body can be ensured and the green body is not cracked during the green body pressing, the existence of pores in the green body is reduced, and the ceramic sintering is facilitated to reach higher densification degree;
fourthly, sintering the blank body step by step in an oxygen protective atmosphere by adopting a common tube furnace during sintering, and firstly raising the temperature to a higher temperature to promote bismuth oxide to generate a liquid phase, thereby being beneficial to ceramic densification; then sintering at a lower temperature, adopting an embedding process, reducing the volatilization of Bi element, ensuring the purity of a ceramic phase, adopting a method of quickly heating to reach the sintering temperature during sintering and quickly cooling to room temperature after the temperature preservation is finished, reducing the time of a blank body existing in an unstable phase temperature interval, reducing the impurity phase content of the ceramic, ensuring the purity of the ceramic phase, and being beneficial to the display of the ferroelectric property of the ceramic.
The invention can obtain the high-purity high-density bismuth ferrite-based ceramic.
Drawings
FIG. 1 shows Bi prepared in example one0.89Nd0.1Sm0.01Fe0.99Ti0.01O3XRD pattern of the ceramic;
FIG. 2 shows Bi prepared in example one0.89Nd0.1Sm0.01Fe0.99Ti0.01O3The hysteresis loop map of the ceramic comprises a curve (I) for testing the field intensity of 180kV/cm and a curve (II) for testing the field intensity of 200 kV/cm;
FIG. 3 is an XRD spectrum, and Curve 1 in FIG. 3 is Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3XRD profile of ceramic, Curve 2 is Bi prepared in example three0.85Nd0.15Fe0.99Zr0.01O3XRD profile of the ceramic;
FIG. 4 is a graph of the hysteresis loop of the ceramic, wherein the curve (i) is Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3The hysteresis loop of the ceramic at a field strength of 180kV/cm, curve c, is Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3The electric hysteresis loop of the ceramic at the field strength of 210kV/cm is shown as the curve II of the Bi prepared in the third example0.85Nd0.15Fe0.99Zr0.01O3The electric hysteresis loop of the ceramic under the field intensity of 180 kV/cm;
FIG. 5 shows Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3Ceramics and Bi prepared in example III0.85Nd0.15Fe0.99Zr0.01O3Leakage current test of ceramics, wherein "■" represents Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3Ceramic, "●" is Bi prepared in example three0.85Nd0.15Fe0.99Zr0.01O3The test field strengths of the ceramics are respectively 50kV/cm, 100kV/cm, 150kV/cm and 180 kV/cm.
Detailed Description
The technical scheme of the invention comprises but is not limited to the following specific embodiments and any combination of the specific embodiments.
The first embodiment is as follows: the chemical general formula of the high-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic is as follows: bi1-xRexFe1-yByO3Wherein 0 is<x≤0.3，0<y is less than or equal to 0.1, x and y are mole fractions, Re is a rare earth element, and the rare earth element is one or a mixture of more of praseodymium element, neodymium element and samarium element; b is a high valence transition metal element, and the high valence transition metal element is one or a mixture of molybdenum, zirconium and titanium; bi is bismuth; the Fe is iron element.
The second embodiment is as follows: the embodiment is a preparation method of high-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic, which is completed according to the following steps:
firstly, weighing materials:
firstly, Bi is according to a chemical general formula1-xRexFe1-yByO3Weighing bismuth oxide, ferric oxide, rare earth oxide and high-valence transition metal oxide powder; wherein 0<x≤0.3，0<y is less than or equal to 0.1, and x and y are mole fractions;
② weighing bismuth oxide again;
the molar ratio of the bismuth oxide weighed in the first step to the bismuth oxide weighed in the first step is (0.01-0.1): 1;
putting the powder of the bismuth oxide, the ferric oxide, the rare earth oxide and the transition metal oxide weighed in the first step and the first step into a ball milling tank, adding a ball milling medium, namely absolute ethyl alcohol and milling balls, and mixing the milling balls by using a high-energy planetary ball mill to obtain a mixture after ball milling;
secondly, drying the mixture subjected to ball milling, and sieving the dried mixture by using a 100-mesh sieve to obtain a raw material mixture with the particle size smaller than 100 meshes;
thirdly, biscuit forming:
firstly, adding a raw material mixture with the particle size of less than 100 meshes and a binder aqueous solution into an agate mortar for grinding and granulation, and then sieving the mixture through a sieve with 150 meshes to 200 meshes to obtain raw material mixed powder with the particle size of 150 meshes to 200 meshes;
the mass ratio of the raw material mixture with the particle size smaller than 100 meshes to the binder in the binder aqueous solution in the third step is (19-49): 1;
secondly, adding the raw material mixed powder with the particle size of 150-200 meshes into a round steel mould with the diameter of 10-30 mm, and maintaining the pressure at 400-700 MPa to obtain a compact blank;
thirdly, heating the compact blank to 200-300 ℃ at the heating rate of 1-2 ℃/min, heating to 500-550 ℃ at the heating rate of 0.5-1 ℃/min, preserving heat at 500-550 ℃ for 1-2 h, cooling to room temperature at the cooling rate of 5-10 ℃/min, and discharging the glue from the blank to obtain a blank after discharging the glue;
fourthly, sintering the ceramic:
firstly, heating the blank after the glue removal to 850-900 ℃ in an oxygen atmosphere, then preserving heat, then cooling to 770-870 ℃, preserving heat, and finally rapidly cooling to room temperature to obtain the high-purity and high-density A/B multi-ion co-doped bismuth ferrite-based ceramic.
In the first step of the embodiment, bismuth oxide is weighed in a molar ratio excess of 1% -10% (namely, the molar ratio of bismuth oxide weighed in the first step to bismuth oxide weighed in the first step is (0.01-0.1): 1), because the Bi element is volatile in the high-temperature sintering process, the excess bismuth oxide can compensate the loss of the Bi element in the high-temperature sintering process, and the purity of the phase is ensured.
In the third step of the embodiment, the purpose of granulating the raw material powder is to facilitate powder compression molding, the granulated powder has uniform particle size and good fluidity, the compactness of the blank body can be ensured and the blank body does not crack when the blank body is compressed, the existence of pores in the blank body is reduced, and the ceramic sintering is facilitated to achieve high densification degree.
In the fourth step of the embodiment, a common tube furnace is adopted to perform fractional sintering under the oxygen protective atmosphere, and the volatilization of Bi element can be reduced by adopting the embedding process; the method of rapidly heating to reach the sintering temperature and rapidly cooling to room temperature after the heat preservation is finished is adopted, so that the time of a blank body existing in an unstable phase temperature interval is reduced, the impurity phase content of the ceramic is reduced, and the purity of the ceramic phase is ensured; meanwhile, liquid phase appears at the sintering temperature, and the densification of the ceramic is promoted.
The embodiment can obtain the high-purity high-density bismuth ferrite-based ceramic.
The third concrete implementation mode: the present embodiment is different from the second embodiment in that: in the step one, the ball-material ratio is (10-15): 1, the ball-milling speed is 200 r/min-400 r/min, and the ball-milling time is 12 h-24 h.
The other steps are the same as those in the second embodiment.
The fourth concrete implementation mode: the present embodiment differs from the second to third embodiments in that: the rare earth oxide in the first step is one or a mixture of praseodymium oxide, neodymium oxide and samarium oxide. The other steps are the same as those in the second to third embodiments.
The fifth concrete implementation mode: the second to fourth embodiments are different from the first to fourth embodiments in that: the high valence transition metal oxide powder in the first step is one or a mixture of molybdenum oxide, zirconium oxide and titanium oxide. The other steps are the same as those in the second to fourth embodiments.
The sixth specific implementation mode: the second to fifth embodiments are different from the first to fifth embodiments in that: the aqueous solution of the binder in the third step is aqueous solution of polyvinyl alcohol; the mass ratio of polyvinyl alcohol to deionized water in the polyvinyl alcohol aqueous solution is (9-19): 1. The other steps are the same as those in the second to fifth embodiments.
The seventh embodiment: the present embodiment differs from one of the second to sixth embodiments in that: and (5) drying the ball-milled mixture in the second step for 12-24 h under vacuum pressure and constant temperature under the conditions that the vacuum degree is-0.05-0.08 MPa and the temperature is 60-80 ℃. The other steps are the same as in embodiments two to six.
The specific implementation mode is eight: the second embodiment differs from the first embodiment in that: and step three, the pressure maintaining time is 3-5 min. The other steps are the same as those in the second to seventh embodiments.
The specific implementation method nine: the second to eighth differences from the first embodiment are as follows: in the fourth step, the blank after the glue discharging is firstly heated to 850-900 ℃ from the room temperature at the heating rate of 10-30 ℃/min under the oxygen atmosphere, then the temperature is preserved for 1-10 min, then the temperature is reduced to 770-870 ℃ at the cooling rate of 10-30 ℃/min, and finally the temperature is preserved for 1-12 h. The other steps are the same as those in the second to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from the second to ninth embodiments in that: and finally, in the fourth step, the mixture is rapidly cooled to room temperature at a cooling rate of 10-30 ℃/min. The other steps are the same as in the second to ninth embodiments.
The following specific examples are given by way of illustration of the embodiments of the present invention and are intended to provide detailed illustrations and specific procedures, but the scope of the present invention is not limited to the following examples.
The first embodiment is as follows: the chemical general formula of the high-purity and high-density A/B site multi-ion co-doped bismuth ferrite-based ceramic is as follows: bi1-xRexFe1-yByO3Wherein x is 0.11, y is 0.01, x and y are mole fractions, and Re is a rare earth element which is a mixture of neodymium element and samarium element; b is a high valence transition metal element, and the high valence transition metal element is a titanium element; bi is bismuth; fe is an iron element, namely the chemical general formula of the high-purity high-density A/B site multi-ion co-doped bismuth ferrite-based ceramic is Bi0.89Nd0.1Sm0.01Fe0.99Ti0.01O3The specific preparation method comprises the following steps:
firstly, weighing materials:
firstly, according to the chemical general formula Bi0.89Nd0.1Sm0.01Fe0.99Ti0.01O3Weighing bismuth oxide, ferric oxide, neodymium oxide, samarium oxide and titanium oxide according to a stoichiometric ratio;
② weighing bismuth oxide again;
the molar ratio of the bismuth oxide weighed in the first step to the bismuth oxide weighed in the first step is 0.03: 1;
putting the bismuth oxide, the iron oxide, the neodymium oxide, the samarium oxide and the titanium oxide powder weighed in the first step and the first step into a ball milling tank, adding a ball milling medium, namely absolute ethyl alcohol and milling balls, and mixing the milling balls by using a high-energy planetary ball mill to obtain a ball-milled mixture;
step one, the ball-material ratio is 13:1, the ball-milling speed is 300r/min, and the ball-milling time is 24 hours;
secondly, drying the ball-milled mixture for 12 hours under vacuum pressure reduction and constant temperature under the conditions that the vacuum degree is-0.05 MPa to-0.08 MPa and the temperature is 80 ℃, and sieving the dried mixture by using a 100-mesh sieve to obtain a raw material mixture with the particle size of less than 100 meshes;
thirdly, biscuit forming:
firstly, putting a raw material mixture with the particle size of less than 100 meshes into an agate mortar for grinding, dropwise adding an aqueous solution of a binder into the raw material mixture with the particle size of less than 100 meshes in batches, dropwise adding 5 drops each time, continuing grinding for 4min after each dropwise addition, then dropwise adding the mixture until the dropwise adding of the aqueous solution of the binder is completed, and sieving the mixture through a sieve of 150 meshes to 200 meshes to obtain raw material mixed powder with the particle size of 150 meshes to 200 meshes;
the aqueous solution of the binder in the third step is aqueous solution of polyvinyl alcohol; the mass ratio of polyvinyl alcohol to deionized water in the polyvinyl alcohol aqueous solution is 19: 1;
the mass ratio of the raw material mixture with the particle size of less than 100 meshes to the binder in the binder aqueous solution in the third step is 49: 1;
secondly, adding the raw material mixed powder with the particle size of 150-200 meshes into a round steel mould with the diameter of 10mm, and maintaining the pressure for 3min under the pressure of 600MPa to obtain a compact blank;
thirdly, heating the compact blank from room temperature to 300 ℃ at the heating rate of 1 ℃/min, heating to 550 ℃ at the heating rate of 0.5 ℃/min, preserving heat at 550 ℃ for 1h, and cooling to room temperature at the cooling rate of 5 ℃/min to finish blank discharging to obtain a blank after discharging;
fourthly, sintering the ceramic:
firstly, heating the blank after glue discharging from room temperature to 900 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, then preserving heat for 1min, then cooling to 870 ℃ at the cooling rate of 10 ℃/min, preserving heat for 3h, and finally cooling to room temperature at the cooling rate of 20 ℃/min to obtain Bi0.89Nd0.1Sm0.01Fe0.99Ti0.01O3A ceramic.
FIG. 1 shows Bi prepared in example one0.89Nd0.1Sm0.01Fe0.99Ti0.01O3XRD pattern of the ceramic;
as can be seen from FIG. 1, Bi prepared in example one0.89Nd0.1Sm0.01Fe0.99Ti0.01O3The ceramic has rhombohedral phase (R3c) structure and no obvious impurityThe phase exists in a homogeneous state and has high phase purity.
FIG. 2 shows Bi prepared in example one0.89Nd0.1Sm0.01Fe0.99Ti0.01O3The hysteresis loop map of the ceramic comprises a curve (I) for testing the field intensity of 180kV/cm and a curve (II) for testing the field intensity of 200 kV/cm;
as can be seen from FIG. 2, Bi prepared in example one0.89Nd0.1Sm0.01Fe0.99Ti0.01O3The ceramic has a saturated electric hysteresis loop, the loop shows good squareness, the ceramic has excellent ferroelectric property, and the residual polarization P is under the test field strength of 200kV/cmrReaches 45 mu C cm-2。
Example two: the chemical general formula of the high-purity and high-density A/B site multi-ion co-doped bismuth ferrite-based ceramic is as follows: bi1-xRexFe1-yByO3Wherein x is 0.15, y is 0.01, x and y are mole fractions, and Re is a rare earth element which is neodymium element; b is a high valence transition metal element, and the high valence transition metal element is a molybdenum element; bi is bismuth; fe is an iron element, namely the chemical general formula of the high-purity high-density A/B site multi-ion co-doped bismuth ferrite-based ceramic is Bi0.85Nd0.15Fe0.99Mo0.01O3The specific preparation method comprises the following steps:
firstly, weighing materials:
firstly, according to the chemical general formula Bi0.85Nd0.15Fe0.99Mo0.01O3Weighing bismuth oxide, ferric oxide, neodymium oxide and molybdenum oxide according to a stoichiometric ratio;
② weighing bismuth oxide again;
the molar ratio of the bismuth oxide weighed in the first step to the bismuth oxide weighed in the first step is 0.03: 1;
putting the bismuth oxide, the ferric oxide, the neodymium oxide and the molybdenum oxide powder weighed in the first step and the first step into a ball milling tank, adding a ball milling medium, namely absolute ethyl alcohol and milling balls, and mixing the milling balls by using a high-energy planetary ball mill to obtain a ball-milled mixture;
step one, the ball-material ratio is 13:1, the ball-milling speed is 300r/min, and the ball-milling time is 24 hours;
secondly, drying the ball-milled mixture for 24 hours under vacuum pressure reduction and constant temperature under the conditions that the vacuum degree is-0.05 MPa to-0.08 MPa and the temperature is 80 ℃, and sieving the dried mixture by using a 100-mesh sieve to obtain a raw material mixture with the particle size of less than 100 meshes;
thirdly, biscuit forming:
firstly, putting a raw material mixture with the particle size of less than 100 meshes into an agate mortar for grinding, dropwise adding an aqueous solution of a binder into the raw material mixture with the particle size of less than 100 meshes in batches, dropwise adding 5 drops each time, continuing grinding for 4min after each dropwise addition, then dropwise adding the mixture until the dropwise adding of the aqueous solution of the binder is completed, and sieving the mixture through a sieve of 150 meshes to 200 meshes to obtain raw material mixed powder with the particle size of 150 meshes to 200 meshes;
the aqueous solution of the binder in the third step is aqueous solution of polyvinyl alcohol; the mass ratio of polyvinyl alcohol to deionized water in the polyvinyl alcohol aqueous solution is 19: 1;
the mass ratio of the raw material mixture with the particle size of less than 100 meshes to the binder in the binder aqueous solution in the third step is 49: 1;
secondly, adding the raw material mixed powder with the particle size of 150-200 meshes into a round steel mould with the diameter of 10mm, and maintaining the pressure for 3min under the pressure of 600MPa to obtain a compact blank;
thirdly, heating the compact blank from room temperature to 300 ℃ at the heating rate of 1 ℃/min, heating to 550 ℃ at the heating rate of 0.5 ℃/min, preserving heat at 550 ℃ for 1h, and cooling to room temperature at the cooling rate of 5 ℃/min to finish blank discharging to obtain a blank after discharging;
fourthly, sintering the ceramic:
firstly, heating the blank after glue discharging from room temperature to 870 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, then preserving heat for 1min, then cooling to 830 ℃ at the cooling rate of 10 ℃/min, preserving heat for 3h, and finally cooling to room temperature at the cooling rate of 10 ℃/min to obtain Bi0.85Nd0.15Fe0.99Mo0.01O3A ceramic.
Example three: the chemical general formula of the high-purity and high-density A/B site multi-ion co-doped bismuth ferrite-based ceramic is as follows: bi1-xRexFe1-yByO3Wherein x is 0.15, y is 0.01, x and y are mole fractions, and Re is a rare earth element which is neodymium element; b is a high valence transition metal element, and the high valence transition metal element is a zirconium element; bi is bismuth; fe is an iron element, namely the chemical general formula of the high-purity high-density A/B site multi-ion co-doped bismuth ferrite-based ceramic is Bi0.85Nd0.15Fe0.99Zr0.01O3The specific preparation method comprises the following steps:
firstly, weighing materials:
firstly, according to the chemical general formula Bi0.85Nd0.15Fe0.99Zr0.01O3Weighing bismuth oxide, ferric oxide, neodymium oxide and zirconium oxide according to a stoichiometric ratio;
② weighing bismuth oxide again;
the molar ratio of the bismuth oxide weighed in the first step to the bismuth oxide weighed in the first step is 0.03: 1;
putting the bismuth oxide, the ferric oxide, the neodymium oxide and the zirconium oxide powder weighed in the first step and the first step into a ball milling tank, adding a ball milling medium, namely absolute ethyl alcohol, and milling balls, and then mixing the anhydrous ethyl alcohol and the milling balls by using a high-energy planetary ball mill to obtain a ball-milled mixture;
step one, the ball-material ratio is 13:1, the ball-milling speed is 300r/min, and the ball-milling time is 24 hours;
secondly, drying the ball-milled mixture for 24 hours under vacuum pressure reduction and constant temperature under the conditions that the vacuum degree is-0.05 MPa to-0.08 MPa and the temperature is 80 ℃, and sieving the dried mixture by using a 100-mesh sieve to obtain a raw material mixture with the particle size of less than 100 meshes;
thirdly, biscuit forming:
firstly, putting a raw material mixture with the particle size of less than 100 meshes into an agate mortar for grinding, dropwise adding an aqueous solution of a binder into the raw material mixture with the particle size of less than 100 meshes in batches, dropwise adding 5 drops each time, continuing grinding for 4min after each dropwise addition, then dropwise adding the mixture until the dropwise adding of the aqueous solution of the binder is completed, and sieving the mixture through a sieve of 150 meshes to 200 meshes to obtain raw material mixed powder with the particle size of 150 meshes to 200 meshes;
the aqueous solution of the binder in the third step is aqueous solution of polyvinyl alcohol; the mass ratio of polyvinyl alcohol to deionized water in the polyvinyl alcohol aqueous solution is 19: 1;
the mass ratio of the raw material mixture with the particle size of less than 100 meshes to the binder in the binder aqueous solution in the third step is 49: 1;
secondly, adding the raw material mixed powder with the particle size of 150-200 meshes into a round steel mould with the diameter of 10mm, and maintaining the pressure for 3min under the pressure of 600MPa to obtain a compact blank;
thirdly, heating the compact blank from room temperature to 300 ℃ at the heating rate of 1 ℃/min, heating to 550 ℃ at the heating rate of 0.5 ℃/min, preserving heat at 550 ℃ for 1h, and cooling to room temperature at the cooling rate of 5 ℃/min to finish blank discharging to obtain a blank after discharging;
fourthly, sintering the ceramic:
firstly, heating the blank after glue discharging from room temperature to 870 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, then preserving heat for 1min, then cooling to 830 ℃ at the cooling rate of 10 ℃/min, preserving heat for 3h, and finally cooling to room temperature at the cooling rate of 10 ℃/min to obtain Bi0.85Nd0.15Fe0.99Zr0.01O3A ceramic.
FIG. 3 is an XRD spectrum, and Curve 1 in FIG. 3 is Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3XRD profile of ceramic, Curve 2 is Bi prepared in example three0.85Nd0.15Fe0.99Zr0.01O3XRD profile of the ceramic;
as can be seen from FIG. 3, Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3Ceramics and Bi prepared in example III0.85Nd0.15Fe0.99Zr0.01O3The ceramic is formed by coexistence of rhombohedral phase (R3c) and orthorhombic phase (Pbnm), and has MPB structure, wherein rhombohedral phase content is high, and no obvious impurity phase exists.
FIG. 4 is a graph of the hysteresis loop of the ceramic, wherein the curve (i) is Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3The hysteresis loop of the ceramic at a field strength of 180kV/cm, curve c, is Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3The electric hysteresis loop of the ceramic at the field strength of 210kV/cm is shown as the curve II of the Bi prepared in the third example0.85Nd0.15Fe0.99Zr0.01O3The electric hysteresis loop of the ceramic under the field intensity of 180 kV/cm;
FIG. 5 shows Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3Ceramics and Bi prepared in example III0.85Nd0.15Fe0.99Zr0.01O3Leakage current test of ceramics, wherein "■" represents Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3Ceramic, "●" is Bi prepared in example three0.85Nd0.15Fe0.99Zr0.01O3The test field strengths of the ceramics are respectively 50kV/cm, 100kV/cm, 150kV/cm and 180 kV/cm.
As can be seen from the curves (r) and (r) in FIG. 4, Bi prepared in example two0.85Nd0.15Fe0.99Mo0.01O3Ceramics and Bi prepared in example III0.85Nd0.15Fe0.99Zr0.01O3The ceramic has a saturated hysteresis loop. At the field intensity of 180kV/cm, Bi0.85Nd0.15Fe0.99Zr0.01O3The remanent polarization of the ceramic is greater than Bi0.85Nd0.15Fe0.99Mo0.01O3Remanent polarization of the ceramic. However, as can be seen from the leakage current test of FIG. 5, Bi is present at the same field strength0.85Nd0.15Fe0.99Zr0.01O3Ceramic funnelThe current is also larger than Bi0.85Nd0.15Fe0.99Mo0.01O3The leakage current of ceramics is not consistent with the commonly accepted relationship between ferroelectric polarization and leakage current, and it is generally accepted that the larger leakage current is not favorable for the expression of ferroelectric polarization. However, this result can indicate that the magnitude of the leakage current in the bismuth ferrite-based ceramic is not a critical factor affecting the ferroelectric properties thereof, and a larger leakage current can still exhibit good ferroelectric properties.
For curves (r) and (c) in FIG. 4, Bi is present at a field strength of 180kV/cm0.85Nd0.15Fe0.99Mo0.01O3The residual polarization is small, and the curve is approximately linear; and Bi is present at a field strength of 210kV/cm0.85Nd0.15Fe0.99Mo0.01O3Remanent polarization PrReach 44 mu C cm-2The curves exhibit good squareness. By combining the curves of the first, the second and the third, the molybdenum doped bismuth ferrite based ceramic can show better ferroelectric property only under higher electric field, and the zirconium doped bismuth ferrite based ceramic can reach saturation of electric hysteresis loop under lower electric field. The result is probably related to different degrees of difficulty of the electric domain of the bismuth ferrite-based ceramic polarization doped with different elements to overturn under the action of an electric field, the energy required by the electric domain overturn of the molybdenum element-doped bismuth ferrite-based ceramic is higher, and the higher electric field is required to provide the energy required by the electric domain overturn. The zirconium element can reduce the activation energy required by the bismuth ferrite-based ceramic electric domain inversion, and the polarization curve can be saturated under a lower electric field.

Claims (4)

1. A preparation method of high-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic is characterized in that the preparation method of the high-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic is completed according to the following steps:
firstly, weighing materials:
firstly, Bi is according to a chemical general formula1-xRexFe1-yByO3Weighing bismuth oxide, ferric oxide, rare earth oxide and high-valence transition metal oxide powder; wherein0<x≤0.3，0<y is less than or equal to 0.1, and x and y are mole fractions;
the rare earth oxide in the first step is one or a mixture of praseodymium oxide, neodymium oxide and samarium oxide;
the high valence transition metal oxide powder in the first step is one or a mixture of molybdenum oxide, zirconium oxide and titanium oxide;
weighing bismuth oxide again:
the molar ratio of the bismuth oxide weighed in the first step to the bismuth oxide weighed in the first step is (0.01-0.1): 1;
putting the powder of the bismuth oxide, the ferric oxide, the rare earth oxide and the transition metal oxide weighed in the first step and the first step into a ball milling tank, adding a ball milling medium, namely absolute ethyl alcohol and milling balls, and mixing the milling balls by using a high-energy planetary ball mill to obtain a mixture after ball milling;
secondly, drying the ball-milled mixture for 12 to 24 hours under vacuum pressure reduction and constant temperature under the conditions that the vacuum degree is-0.05 to-0.08 MPa and the temperature is 60 to 80 ℃, and then sieving the mixture by using a 100-mesh sieve to obtain a raw material mixture with the particle size of less than 100 meshes;
thirdly, biscuit forming:
firstly, adding a raw material mixture with the particle size of less than 100 meshes and a binder aqueous solution into an agate mortar for grinding and granulation, and then sieving the mixture through a sieve with 150 meshes to 200 meshes to obtain raw material mixed powder with the particle size of 150 meshes to 200 meshes;
the aqueous solution of the binder in the third step is aqueous solution of polyvinyl alcohol; the mass ratio of polyvinyl alcohol to deionized water in the polyvinyl alcohol aqueous solution is (9-19) to 1;
the mass ratio of the raw material mixture with the particle size smaller than 100 meshes to the binder in the binder aqueous solution in the third step is (19-49): 1;
secondly, adding the raw material mixed powder with the particle size of 150-200 meshes into a round steel mould with the diameter of 10-30 mm, and maintaining the pressure at 400-700 MPa to obtain a compact blank;
thirdly, heating the compact blank to 200-300 ℃ at the heating rate of 1-2 ℃/min, heating to 500-550 ℃ at the heating rate of 0.5-1 ℃/min, preserving heat at 500-550 ℃ for 1-2 h, cooling to room temperature at the cooling rate of 5-10 ℃/min, and discharging the glue from the blank to obtain a blank after discharging the glue;
fourthly, sintering the ceramic:
firstly, heating the blank after the glue removal to 850-900 ℃ in an oxygen atmosphere, then preserving heat, then cooling to 770-870 ℃, preserving heat, and finally rapidly cooling to room temperature to obtain high-purity and high-density A/B multi-ion co-doped bismuth ferrite-based ceramic;
in the fourth step, the blank after the glue discharging is firstly heated to 850-900 ℃ from the room temperature at the heating rate of 10-30 ℃/min under the oxygen atmosphere, then the temperature is preserved for 1-10 min, then the temperature is reduced to 770-870 ℃ at the cooling rate of 10-30 ℃/min, and finally the temperature is preserved for 1-12 h.
2. The preparation method of the high-purity high-density A/B site multi-ion co-doped bismuth ferrite-based ceramic according to claim 1 is characterized in that in the step one, the ball-milling ratio is (10-15): 1, the ball-milling speed is 200 r/min-400 r/min, and the ball-milling time is 12 h-24 h.
3. The preparation method of the high-purity high-density A/B site multi-ion co-doped bismuth ferrite-based ceramic according to claim 1, wherein the pressure maintaining time in the third step is 3-5 min.
4. The preparation method of the high-purity high-density A/B site multi-ion co-doped bismuth ferrite-based ceramic according to claim 1, characterized in that in the fourth step, the ceramic is rapidly cooled to room temperature at a cooling rate of 10 ℃/min to 30 ℃/min.
CN202010421696.0A 2020-05-18 2020-05-18 High-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic and preparation method thereof Active CN111592346B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010421696.0A CN111592346B (en) 2020-05-18 2020-05-18 High-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010421696.0A CN111592346B (en) 2020-05-18 2020-05-18 High-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111592346A CN111592346A (en) 2020-08-28
CN111592346B true CN111592346B (en) 2022-02-22

Family

ID=72180538

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010421696.0A Active CN111592346B (en) 2020-05-18 2020-05-18 High-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111592346B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112225550B (en) * 2020-09-11 2022-10-04 广东天瞳科技有限公司 Piezoelectric ceramic material, preparation method thereof and piezoelectric ceramic sensor
CN113292340B (en) * 2021-06-02 2022-08-26 哈尔滨工业大学 High-piezoelectricity low-loss donor-acceptor co-doped piezoelectric ceramic, and preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429642A (en) * 2008-12-05 2009-05-13 华中科技大学 BiFeO3 target and film production method
KR101122631B1 (en) * 2010-09-17 2012-03-09 한국기계연구원 Complex perovskite ceramics and films with superior room temperature multiferroic properties, and the fabrication method thereof
CN105060882A (en) * 2015-07-23 2015-11-18 罗美柏 Piezoceramic material and preparation method therefor
CN106565228B (en) * 2016-11-14 2020-07-28 郑州轻工业学院 Europium and zirconium codoped bismuth ferrite multiferroic ceramic and preparation method thereof
CN109704765A (en) * 2019-03-07 2019-05-03 哈尔滨工业大学 High densification ferroelectric ceramics and preparation method thereof with quasi- homotype crystal phase structure

Also Published As

Publication number Publication date
CN111592346A (en) 2020-08-28

Similar Documents

Publication Publication Date Title
CN111592346B (en) High-purity high-compactness A/B site multi-ion co-doped bismuth ferrite-based ceramic and preparation method thereof
JP7047530B2 (en) Ferrite Sintered Magnet and Ferrite Sintered Magnet Manufacturing Method
CN106565228B (en) Europium and zirconium codoped bismuth ferrite multiferroic ceramic and preparation method thereof
CN104496443A (en) High magnetic-energy-product M type calcium series permanent magnetic ferrite material and preparation method thereof
KR101253768B1 (en) Ferrite material
CN105601264A (en) Preparation method of high-densification multiferroic (1-y)BiFeO[3-y]Bi[1-x]RxFeO3 composite ceramic
US20210380486A1 (en) Low loss power ferrites and method of manufacture
CN114716248A (en) High-energy-storage-property rare earth-doped tungsten bronze structure ceramic material and preparation method thereof
CN103964830A (en) Method for preparing permanent magnetic ferrite by low-temperature sintering
KR20150048256A (en) Magnet powders, production methods thereof, and magnets including the same
CN110451948A (en) It is a kind of for communication isolator and the Ferrite Material of circulator and preparation method thereof
CN112562950B (en) Ferrite sintered magnet
JP7347296B2 (en) Ferrite sintered magnets and rotating electrical machines
CN111161949B (en) YCe co-doped nanocrystalline rare earth permanent magnet and preparation method thereof
CN110128133B (en) Barium titanate calcium based leadless piezoelectric ceramic and preparation method thereof
CN112851329B (en) Bismuth ferrite lead titanate-based functional ceramic material and preparation method thereof
JPH0261121B2 (en)
KR102683577B1 (en) Method for preparing ferrite sintered magnet
Peloschek et al. High-permeability MnZn ferrites with flat µ-T curves
CN104944944A (en) Re2x/3(Ba0.06Bi0.47Na0.47)1-xMeyTi1-yO3 leadless antiferroelectric high-energy density ceramic and preparation method thereof
CN116514547B (en) Lead ytterbium niobate-based antiferroelectric ceramic material and preparation method and application thereof
KR20150073759A (en) Process for preparing sintered magnets
CN110498676B (en) Nano ceramic and preparation method thereof
JPH0761821A (en) Production of garnet-type magnetic material
JP2022138110A (en) Sintered ferrite magnet and manufacturing 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