CN106587994B - A kind of low temperature cold sintering preparation method of barium titanate ferroelectric ceramics - Google Patents

A kind of low temperature cold sintering preparation method of barium titanate ferroelectric ceramics Download PDF

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CN106587994B
CN106587994B CN201611169690.9A CN201611169690A CN106587994B CN 106587994 B CN106587994 B CN 106587994B CN 201611169690 A CN201611169690 A CN 201611169690A CN 106587994 B CN106587994 B CN 106587994B
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ferroelectric ceramics
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CN106587994A (en
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王诗阳
傅宇东
朱小硕
冷科
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Harbin Engineering University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
    • 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
    • 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
    • C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum

Abstract

The present invention is to provide a kind of low temperature cold sintering preparation methods of barium titanate ferroelectric ceramics.1. by Ba (OH)2And TiO2It is dissolved in deionized water；2. by BaTiO3Nanometer grade powder and BaTiO3Ba (OH) prepared in 25wt.% step 1 is added according to the ratio of mass ratio 1:1 in sub-micron powder2/TiO2Suspension grinds 0.5-1h in mortar；3. by BaTiO3Mixed slurry pours into mold, is cold-pressed in room temperature environment, on electric heating press machine, pressure 450-500MPa, dwell time 10-20min；Hereafter, it keeps pressure constant, heating temperature is increased to 180-200 DEG C, 5-10 DEG C of heating rate/min, soaking time 3h；4.BaTiO3Ceramics preparative green body is in 200 DEG C of drying 12-18h；5. by the BaTiO after drying3Ceramics preparative green body is sintered at 850-950 DEG C.Present invention process is simple, environmental-friendly, energy consumption is extremely low, can become underwater acoustic transducer BaTiO3The ideal preparation method of ferroelectric ceramics has wide industrial application prospect.

Description

A kind of low temperature cold sintering preparation method of barium titanate ferroelectric ceramics
Technical field
The present invention is to provide a kind of sintering preparation methods of barium titanate ferroelectric ceramics.
Background technique
Ferroelectric ceramics has the performances such as complicated dielectric, piezoelectricity, photoelectricity and microwave absorption, can be applied to electronic work The fields such as industry, aerospace, Underwater Acoustics Engineering.Barium titanate (BaTiO3) it is exactly wherein one of most widely used ferroelectric ceramics. BaTiO3It is a kind of with typical perovskite type structure (ABO3) ferroelectric, lower than having 5 kinds of inhomogeneities in 1618 DEG C of warm areas The crystal structure of type, i.e. six sides, cube, cubic, orthogonal, trigonal crystal structure.In Curie temperature TcAt=120 DEG C or so, BaTiO3's Phase structure is tetragonal phase by cubic phase transition, spontaneous polarization (its polarization direction is along c-axis direction) occurs, becomes ferroelectricity from paraelectric phase Phase, to have excellent ferroelectricity and piezoelectric property.BaTiO3Also have the characteristics that high dielectric constant, good insulation performance, It has been used to prepare the electronic components such as multilayer ceramic capacitor (MLCC), dynamic RAM (DRAM), node amplifier. BaTiO3As a kind of Typical dielectric materials, absorbs, decays by electronic polarization, ionic polarization or the interfacial polarization to medium Electromagnetic wave and a kind of microwave absorbing material of great potential.In addition, BaTiO3Or a kind of typical piezoelectric material, can Realize that acoustic vibration signal and electric signal are delicately converted.Therefore, BaTiO3Ceramics can be used as the transmitting of underwater acoustic transducer and connect Device is received, underwater navigation positioning, supersonic sounding and locating fish etc. is carried out and does industry.
BaTiO3The consistency of ceramics is to influence the key factor of its piezoelectric property.For ceramic material, sintering temperature It improves, the extension of soaking time is conducive to it and realizes densification；But the crystallite dimension that will lead to material, which increases with it, (makes dielectric The Key Performance Indicators such as constant are uncontrollable), meanwhile, high temperature sintering will bring great cost loss, constrain it industrially Batch production.Usually, BaTiO3The sintering temperature of ferroelectric ceramics is up to 1300-1400 DEG C.In recent years, researchers couple BaTiO3The low temperature sintering technology of ceramics has carried out continuous exploration.Maiwa et al. is sintered (SPS) work using discharge plasma Skill is prepared for the BaTiO that consistency is greater than 99% under 1000 DEG C of sintering temperatures3Ceramics.Hiofumi et al. uses microwave sintering (MVS) technique is prepared for the BaTiO that consistency is 98.3% under 1320 DEG C of sintering temperatures3Ceramics.M.Peko is using quickly burning (FS) technique is tied, being prepared for consistency in 1300 DEG C of heat preservation 5min is 97.2%BaTiO3Ceramics.X.-H.Wang et al. uses two Step sintering (TSS) technique, two-step sintering minimum temperature are respectively that consistency has finally been made under conditions of 950 DEG C and 900 DEG C 98.0% BaTiO3Ceramics.It can be seen that even if using BaTiO3Nanometer powder and advanced sintering process, fine and close BaTiO3 The sintering temperature of ceramic (about 98%) can only be down to 950-1300 DEG C.
Summary of the invention
The purpose of the present invention is to provide a kind of simple process, environmental-friendly, energy consumption is extremely low, the BaTiO of preparation3Ferroelectricity pottery Porcelain has the low temperature cold sintering preparation method of the barium titanate ferroelectric ceramics of excellent dielectric properties and toughness.
The object of the present invention is achieved like this:
1. by Ba (OH)2And TiO2It is dissolved in deionized water according to the ratio of molar ratio 1.2:1, ultrasonic disperse simultaneously stirs 20- 40min is made Ba (OH)2Concentration is the Ba (OH) of 0.1mol/L2/TiO2Suspension；
2. by BaTiO3Nanometer grade powder and BaTiO3Sub-micron powder is mixed to get mixed according to the ratio of mass ratio 1:1 Powder is closed, according still further to Ba (OH) prepared by mixed-powder and step 12/TiO2The ratio that the mass ratio of suspension is 4:1 is added Suspension grinds 0.5-1h in mortar；
3. by the BaTiO after being ground in step 23Mixed slurry pours into mold, in room temperature environment, electric heating press machine On be cold-pressed, pressure 450-500MPa, dwell time 10-20min；Hereafter, keep pressure constant, by heating temperature liter Up to 180-200 DEG C, 5-10 DEG C of heating rate/min, soaking time 3h；BaTiO is made3The preform blank of ceramics；
4.BaTiO3Ceramics preparative green body is in 200 DEG C of drying 12-18h；
5. by the BaTiO after drying3Ceramics preparative green body is sintered at 850-950 DEG C, and the BaTiO of high-compactness is made3 Ferroelectric ceramics.
The present invention may also include:
1, the sintering is pressureless sintering, and sintering temperature is 850-950 DEG C, and the sintered heat insulating time is 3-4h, heating rate For 5 DEG C/min, sintering atmosphere is argon gas, nitrogen or vacuum.
2, the sintering is hot pressed sintering, and sintering temperature is 800-900 DEG C, and pressuring method is one-way or bi-directional pressurization, is applied Plus-pressure is 30-50MPa, and the sintered heat insulating time is 3-4h, and heating rate is 5 DEG C/min, and sintering atmosphere is argon gas, nitrogen or true It is empty.
3, the sintering is HIP sintering, and sintering temperature is 750-850 DEG C, pressure 50-100MPa, sintered heat insulating Time is 3-4h, and heating rate is 5 DEG C/min.
4, the BaTiO3The purity > 99.5% of nanometer grade powder, average grain diameter 40-60nm, cubic phase；It is described BaTiO3The purity > 99.5% of sub-micron powder, average grain diameter 400-600nm, cubic phase.
For BaTiO3The problem of ferroelectric ceramics sintering temperature height, densification relatively difficult to achieve, the invention proposes one kind BaTiO3The low temperature cold sintering preparation method of ferroelectric ceramics.The BaTiO prepared using hydrothermal synthesis method3Nanometer and submicron powder For starting powder, BaTiO is obtained under the calcined temperature lower than 200 DEG C3The preform blank of ceramics；Then, in extremely low sintering Fine and close BaTiO is prepared at temperature (≤950 DEG C)3Ceramic (consistency > 97.5%)；The BaTiO of preparation3Ferroelectric ceramics has Excellent dielectric properties and toughness.This method simple process, environmental-friendly, energy consumption is extremely low, can become underwater acoustic transducer Use BaTiO3The ideal preparation method of ferroelectric ceramics has wide industrial application prospect.
BaTiO3The frequency range of ferroelectric ceramics dielectric properties test: 1kHz-1MHz；Temperature range: 25-100 DEG C.According to GB/T4742-1984, test b aTiO3The toughness of ferroelectric ceramics.After tested, it is burnt using low temperature cold proposed by the present invention Tie the BaTiO of technique preparation3Ferroelectric ceramics has excellent dielectric properties and fracture toughness, suitable for manufacturing underwater acoustic transducer Core component.
Specific embodiment
The low temperature cold sintering preparation method of underwater acoustic transducer barium titanate ferroelectric ceramics of the invention, in low temperature presintering rank Section, under the evaporation of high pressure, water or aqueous solution and the dissolution precipitation process collective effect of powder granule, is prepared for consistency density The barium titanate preform blank of higher (> 95%).Using pressureless sintering, hot pressed sintering or HIP sintering technique to barium titanate Preform blank carries out low-temperature sintering (≤950 DEG C), can prepare the barium titanate ferroelectric ceramics of consistency higher (> 97.5%), Suitable for manufacturing the core component of underwater acoustic transducer.It illustrates below and the present invention is described in more detail.
Embodiment 1:
By Ba (OH)2And TiO2Powder is placed in solvent according to according to the ratio of molar ratio 1.2:1 (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 20-40min, and the suspension that Ba (OH) 2 concentration is 0.1mol/L is made.
Choosing purity respectively is 99.5%, and average grain diameter is the BaTiO of 40nm3Nanometer grade powder and purity are 99.9%, Average grain diameter is the BaTiO of 400nm3Sub-micron powder calculates institute according to the size for preparing BaTiO3 ceramics and related device The quality for needing BaTiO3 powder, by BaTiO3 nanometer grade powder and BaTiO3 sub-micron powder according to the ratio of mass ratio 1:1, Ba (OH) 2/TiO2 suspension prepared in 25wt.% step 1 is added and grinds 0.5-1h in mortar.
After room temperature is cold-pressed 10min, heat preservation and pressure maintaining 3h, pressure 450MPa at 180 DEG C.By BaTiO3Ceramics preparative green bodies 12h is dried at a temperature of 200 DEG C.
BaTiO3 ceramics preparative green body after drying is subjected to pressureless sintering, technological parameter are as follows: 850 DEG C of sintering temperature, protect Warm time 4h, vacuum degree are 1.3 × 10-2Pa。
BaTiO is made3For the consistency of ceramics up to 97.8%, toughness at room temperature is 6.24kJ/m2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency be respectively 1267,1218, 1180 and 1133；Dielectric loss is respectively 0.025,0.027,0.020 and 0.018.With the raising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increase with it, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant when 10kHz, 100kH and 1MH frequency is respectively 1497,1434,1367 and 1316；Dielectric loss is respectively 0.034,0.035,0.025 and 0.021.
Embodiment 2:
By Ba (OH)2And TiO2Powder is placed in solvent according to according to the ratio of molar ratio 1.2:1 (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 30min, is made Ba (OH)2Concentration is the suspension of 0.1mol/L.
Choosing purity respectively is 99.8%, and average grain diameter is the BaTiO of 50nm3Nanometer grade powder and purity are 99.9%, Average grain diameter is the BaTiO of 500nm3Sub-micron powder.According to the size for preparing BaTiO3 ceramics and related device, institute is calculated The quality for needing BaTiO3 powder, by BaTiO3 nanometer grade powder and BaTiO3 sub-micron powder according to the ratio of mass ratio 1:1, Ba (OH) 2/TiO2 suspension prepared in 25wt.% step 1 is added and grinds 0.5-1h in mortar.
After room temperature is cold-pressed 15min, heat preservation and pressure maintaining 3h, pressure 500MPa at 200 DEG C.By BaTiO3Ceramics preparative green bodies 18h is dried at a temperature of 200 DEG C.
Carry out vacuum non-pressure sintering, technological parameter are as follows: 900 DEG C of sintering temperature, soaking time 3h, vacuum degree is 1.3 × 10- 2Pa。
BaTiO is made3For the consistency of ceramics up to 98.0%, toughness at room temperature is 6.53kJ/m2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency be respectively 1760,1720, 1682 and 1637；Dielectric loss is respectively 0.019,0.027,0.018 and 0.015.With the raising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increase with it, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant when 10kHz, 100kH and 1MH frequency is respectively 2057,1928,1798 and 1630；Dielectric loss is respectively 0.028,0.027,0.025 and 0.017.
Embodiment 3:
By Ba (OH)2And TiO2Powder is placed in solvent according to according to the ratio of molar ratio 1.2:1 (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 40min, is made Ba (OH)2Concentration is the suspension of 0.1mol/L.
Choosing purity respectively is 99.99%, and average grain diameter is the BaTiO of 40nm3Nanometer grade powder and purity are 99.9%, Average grain diameter is the BaTiO of 500nm3Sub-micron powder.According to the size for preparing BaTiO3 ceramics and related device, institute is calculated The quality for needing BaTiO3 powder, by BaTiO3 nanometer grade powder and BaTiO3 sub-micron powder according to the ratio of mass ratio 1:1, Ba (OH) 2/TiO2 suspension prepared in 25wt.% step 1 is added and grinds 0.5-1h in mortar.
After room temperature is cold-pressed 20min, heat preservation and pressure maintaining 3h, pressure 450MPa at 200 DEG C.By BaTiO3Ceramics preparative green bodies 12h is dried at a temperature of 200 DEG C.
Carry out pressureless sintering, technological parameter are as follows: 950 DEG C of sintering temperature, soaking time 3h, argon gas protection.
BaTiO is made3For the consistency of ceramics up to 98.4%, toughness at room temperature is 6.71kJ/m2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency be respectively 2243,2215, 2170 and 3132；Dielectric loss is respectively 0.017,0.025,0.016 and 0.014.With the raising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increase with it, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant when 10kHz, 100kH and 1MH frequency is respectively 2576,2365,2219 and 1940；Dielectric loss is respectively 0.026,0.025,0.023 and 0.016.
Embodiment 4:
By Ba (OH)2And TiO2Powder is placed in solvent according to according to the ratio of molar ratio 1.2:1 (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 30min, is made Ba (OH)2Concentration is the suspension of 0.1mol/L.
Choosing purity respectively is 99.7%, and average grain diameter is the BaTiO of 50nm3Nanometer grade powder and purity are 99.9%, Average grain diameter is the BaTiO of 400nm3Sub-micron powder.According to the size for preparing BaTiO3 ceramics and related device, institute is calculated The quality for needing BaTiO3 powder, by BaTiO3 nanometer grade powder and BaTiO3 sub-micron powder according to the ratio of mass ratio 1:1, Ba (OH) 2/TiO2 suspension prepared in 25wt.% step 1 is added and grinds 0.5-1h in mortar.
After room temperature is cold-pressed 15min, heat preservation and pressure maintaining 3h, pressure 450MPa at 180 DEG C.By BaTiO3Ceramics preparative green bodies 12h is dried at a temperature of 200 DEG C.
Carry out vacuum heating-press sintering, technological parameter are as follows: 800 DEG C of sintering temperature, soaking time 4h, pressure 50MPa, vacuum Degree is 1.3 × 10-2Pa。
BaTiO is made3For the consistency of ceramics up to 97.9%, toughness at room temperature is 6.46kJ/m2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency be respectively 1270,1221, 1189 and 1142；Dielectric loss is respectively 0.025,0.027,0.019 and 0.018.With the raising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increase with it, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant when 10kHz, 100kH and 1MH frequency is respectively 1501,1438,1372 and 1325；Dielectric loss is respectively 0.033,0.035,0.026 and 0.022.
Embodiment 5:
By Ba (OH)2And TiO2Powder is placed in solvent according to according to the ratio of molar ratio 1.2:1 (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 40min, is made Ba (OH)2Concentration is the suspension of 0.1mol/L.
Choosing purity respectively is 99.9%, and average grain diameter is the BaTiO of 40nm3Nanometer grade powder and purity are 99.9%, Average grain diameter is the BaTiO of 500nm3Sub-micron powder.According to the size for preparing BaTiO3 ceramics and related device, institute is calculated The quality for needing BaTiO3 powder, by BaTiO3 nanometer grade powder and BaTiO3 sub-micron powder according to the ratio of mass ratio 1:1, Ba (OH) 2/TiO2 suspension prepared in 25wt.% step 1 is added and grinds 0.5-1h in mortar.
After room temperature is cold-pressed 20min, heat preservation and pressure maintaining 3h, pressure 400MPa at 190 DEG C.By BaTiO3Ceramics preparative green bodies 18h is dried at a temperature of 200 DEG C.
Carry out vacuum heating-press sintering, technological parameter are as follows: 850 DEG C of sintering temperature, soaking time 3h, pressure 40MPa, vacuum Degree is 1.3 × 10-2Pa。
BaTiO is made3For the consistency of ceramics up to 98.1%, toughness at room temperature is 6.64kJ/m2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency be respectively 1762,1723, 1685 and 1641；Dielectric loss is respectively 0.018,0.026,0.017 and 0.015.With the raising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increase with it, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant when 10kHz, 100kH and 1MH frequency is respectively 2060,1931,1800 and 1635；Dielectric loss is respectively 0.027,0.027,0.024 and 0.017.
Embodiment 6:
By Ba (OH)2And TiO2Powder is placed in solvent according to according to the ratio of molar ratio 1.2:1 (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 20min, is made Ba (OH)2Concentration is the suspension of 0.1mol/L.
Choosing purity respectively is 99.99%, and average grain diameter is the BaTiO of 40nm3Nanometer grade powder and purity are 99.9%, Average grain diameter is the BaTiO of 400nm3Sub-micron powder.According to the size for preparing BaTiO3 ceramics and related device, institute is calculated The quality for needing BaTiO3 powder, by BaTiO3 nanometer grade powder and BaTiO3 sub-micron powder according to the ratio of mass ratio 1:1, Ba (OH) 2/TiO2 suspension prepared in 25wt.% step 1 is added and grinds 0.5-1h in mortar.
After room temperature is cold-pressed 20min, heat preservation and pressure maintaining 3h, pressure 450MPa at 180 DEG C.By BaTiO3Ceramics preparative green bodies 18h is dried at a temperature of 200 DEG C.
Carry out hot pressed sintering, technological parameter are as follows: 900 DEG C of sintering temperature, soaking time 3h, pressure 30MPa, argon gas is protected Shield.
BaTiO is made3For the consistency of ceramics up to 98.4%, toughness at room temperature is 6.75kJ/m2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency be respectively 2240,2215, 2166 and 3137；Dielectric loss is respectively 0.017,0.026,0.017 and 0.014.With the raising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increase with it, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant when 10kHz, 100kH and 1MH frequency is respectively 2574,2369,2234 and 1947；Dielectric loss is respectively 0.025,0.026,0.023 and 0.015.
Embodiment 7:
By Ba (OH)2And TiO2Powder is placed in solvent according to according to the ratio of molar ratio 1.2:1 (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 20min, is made Ba (OH)2Concentration is the suspension of 0.1mol/L.
Choosing purity respectively is 99.8%, and average grain diameter is the BaTiO of 40nm3Nanometer grade powder and purity are 99.8%, Average grain diameter is the BaTiO of 500nm3Sub-micron powder.According to the size for preparing BaTiO3 ceramics and related device, institute is calculated The quality for needing BaTiO3 powder, by BaTiO3 nanometer grade powder and BaTiO3 sub-micron powder according to the ratio of mass ratio 1:1, Ba (OH) 2/TiO2 suspension prepared in 25wt.% step 1 is added and grinds 0.5-1h in mortar.
After room temperature is cold-pressed 15min, heat preservation and pressure maintaining 3h, pressure 500MPa at 200 DEG C.By BaTiO3Ceramics preparative green bodies 12h is dried at a temperature of 200 DEG C.
Carry out vacuum HIP sintering, technological parameter are as follows: 800 DEG C of sintering temperature, soaking time 3h, pressure 50MPa, Vacuum degree is 1.3 × 10-2Pa。
BaTiO is made3For the consistency of ceramics up to 98.2%, toughness at room temperature is 6.69kJ/m2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency be respectively 1870,1834, 1802 and 1781；Dielectric loss is respectively 0.017,0.026,0.016 and 0.015.With the raising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increase with it, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant when 10kHz, 100kH and 1MH frequency is respectively 2182,2125,1907 and 1762；Dielectric loss is respectively 0.026,0.028,0.025 and 0.018.
Embodiment 8:
By Ba (OH)2And TiO2Powder is placed in solvent according to according to the ratio of molar ratio 1.2:1 (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 20min, is made Ba (OH)2Concentration is the suspension of 0.1mol/L.
Choosing purity respectively is 99.99%, and average grain diameter is the BaTiO of 50nm3Nanometer grade powder and purity are 99.9%, Average grain diameter is the BaTiO of 400nm3Sub-micron powder.According to the size for preparing BaTiO3 ceramics and related device, institute is calculated The quality for needing BaTiO3 powder, by BaTiO3 nanometer grade powder and BaTiO3 sub-micron powder according to the ratio of mass ratio 1:1, Ba (OH) 2/TiO2 suspension prepared in 25wt.% step 1 is added and grinds 0.5-1h in mortar.
After room temperature is cold-pressed 20min, heat preservation and pressure maintaining 3h, pressure 450MPa at 200 DEG C.By BaTiO3Ceramics preparative green bodies 18h is dried at a temperature of 200 DEG C.
Carry out vacuum HIP sintering, technological parameter are as follows: 850 DEG C of sintering temperature, soaking time 3h, pressure 80MPa, Vacuum degree is 1.3 × 10-2Pa。
BaTiO is made3For the consistency of ceramics up to 98.5%, toughness at room temperature is 6.84kJ/m2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency be respectively 2354,2330, 2297 and 3254；Dielectric loss is respectively 0.018,0.026,0.017 and 0.015.With the raising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increase with it, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant when 10kHz, 100kH and 1MH frequency is respectively 2695,2486,2340 and 2062；Dielectric loss is respectively 0.025,0.026,0.022 and 0.017.

Claims (5)

1. a kind of low temperature cold sintering preparation method of barium titanate ferroelectric ceramics, it is characterized in that:
Step 1. is by Ba (OH)2And TiO2It is dissolved in deionized water according to the ratio of molar ratio 1.2:1, ultrasonic disperse simultaneously stirs 20- 40min is made Ba (OH)2Concentration is the Ba (OH) of 0.1mol/L2/TiO2Suspension；
Step 2. is by BaTiO3Nanometer grade powder and BaTiO3Sub-micron powder is mixed to get mixed according to the ratio of mass ratio 1:1 Powder is closed, according still further to Ba (OH) prepared by mixed-powder and step 12/TiO2The ratio that the mass ratio of suspension is 4:1 is added Suspension grinds 0.5-1h in mortar；
Step 3. by step 2 grind after BaTiO3Mixed slurry pours into mold, in room temperature environment, electric heating press machine On be cold-pressed, pressure 450-500MPa, dwell time 10-20min；Hereafter, keep pressure constant, by heating temperature liter Up to 180-200 DEG C, 5-10 DEG C of heating rate/min, soaking time 3h；BaTiO is made3The preform blank of ceramics；
Step 4.BaTiO3Ceramics preparative green body is in 200 DEG C of drying 12-18h；
Step 5. is by the BaTiO after drying3Ceramics preparative green body is sintered at 850-950 DEG C, is made consistency >'s 97.5% The BaTiO of high-compactness3Ferroelectric ceramics.
2. the low temperature cold sintering preparation method of barium titanate ferroelectric ceramics according to claim 1, it is characterized in that: the sintering It is pressureless sintering, sintering temperature is 850-950 DEG C, and the sintered heat insulating time is 3-4h, and heating rate is 5 DEG C/min, sintering atmosphere For argon gas, nitrogen or vacuum.
3. the low temperature cold sintering preparation method of barium titanate ferroelectric ceramics according to claim 1, it is characterized in that: the sintering It is hot pressed sintering, sintering temperature is 800-900 DEG C, and pressuring method is one-way or bi-directional pressurization, and application pressure is 30-50MPa, is burnt Knot soaking time is 3-4h, and heating rate is 5 DEG C/min, and sintering atmosphere is argon gas, nitrogen or vacuum.
4. the low temperature cold sintering preparation method of barium titanate ferroelectric ceramics according to claim 1, it is characterized in that: the sintering It is HIP sintering, sintering temperature is 750-850 DEG C, pressure 50-100MPa, and the sintered heat insulating time is 3-4h, heating speed Rate is 5 DEG C/min.
5. according to claim 1 to the low temperature cold sintering preparation method of barium titanate ferroelectric ceramics described in 4 any one, feature It is: the BaTiO3The purity > 99.5% of nanometer grade powder, average grain diameter 40-60nm, cubic phase；The BaTiO3Sub-micro The purity > 99.5% of nanoscale powder, average grain diameter 400-600nm, cubic phase.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1275117A (en) * 1998-07-01 2000-11-29 卡伯特公司 Hydrothermal process for making barium titanate powders
CN1428310A (en) * 2001-12-28 2003-07-09 株式会社村田制作所 Method for preparing composite oxide powder and composite oxide powder
CN103342557A (en) * 2013-07-05 2013-10-09 深圳市大富科技股份有限公司 Preparation method of microwave dielectric ceramic material
CN103342383A (en) * 2013-07-05 2013-10-09 深圳市大富科技股份有限公司 Preparation method of microwave dielectric ceramic material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1275117A (en) * 1998-07-01 2000-11-29 卡伯特公司 Hydrothermal process for making barium titanate powders
CN1428310A (en) * 2001-12-28 2003-07-09 株式会社村田制作所 Method for preparing composite oxide powder and composite oxide powder
CN103342557A (en) * 2013-07-05 2013-10-09 深圳市大富科技股份有限公司 Preparation method of microwave dielectric ceramic material
CN103342383A (en) * 2013-07-05 2013-10-09 深圳市大富科技股份有限公司 Preparation method of microwave dielectric ceramic material

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