CN106587994A - Low-temperature cold sintering preparation method of barium titanate ferroelectric ceramic - Google Patents

Low-temperature cold sintering preparation method of barium titanate ferroelectric ceramic Download PDF

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CN106587994A
CN106587994A CN201611169690.9A CN201611169690A CN106587994A CN 106587994 A CN106587994 A CN 106587994A CN 201611169690 A CN201611169690 A CN 201611169690A CN 106587994 A CN106587994 A CN 106587994A
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batio3
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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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    • 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
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Abstract

The invention provides a low-temperature cold sintering preparation method of barium titanate ferroelectric ceramic. The preparation method comprises the following steps: 1, dissolving Ba(OH)2 and TiO2 into deionized water; 2, adding BaTiO3 nano-level powder and BaTiO3 submicron-level powder into 25 percent of Ba(OH)2/TiO2 suspension by weight prepared in the step 1 according to the mass ratio of 1 to 1, and carrying out grinding in a grinding bowl for 0.5 to 1 hour; 3, pouring BaTiO3 mixed slurry into a mold, carrying out cold pressing on an electric heating press in an environment with room temperature till the pressure is 450 to 500 MPa, preserving the pressure for 10 to 20 min, then under a condition of not changing the pressure, heating to 180 to 200 DEG C at the heating rate of 5 to 10 DEG C per minute, and preserving the temperature for 3 hours; 4, drying a BaTiO3 ceramic prefabricated blank at 200 DEG C for 12 to 18 hours; and 5, sintering the dried BaTiO3 ceramic prefabricated blank at 850 to 950 DEG C. The process is simple, environment-friendly and extremely low in energy consumption; the preparation method can be an ideal preparation method of the BaTiO3 ferroelectric ceramic for an underwater acoustic transducer, and has a wide industrial application prospect.

Description

A kind of low temperature cold sintering preparation method of barium titanate ferroelectric ceramicses
Technical field
The present invention is to provide a kind of sintering preparation method of barium titanate ferroelectric ceramicses.
Background technology
Ferroelectric ceramics has the performances such as complicated dielectric, piezoelectricity, photoelectricity and microwave absorption, can apply to electronic work The fields such as industry, Aero-Space, Underwater Acoustics Engineering.Barium titanate (BaTiO3) it is exactly one of wherein most widely used ferroelectric ceramics. BaTiO3It is that one kind has typical perovskite type structure (ABO3) ferroelectric, less 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 TcWhen=120 DEG C or so, BaTiO3's Phase structure is Tetragonal by cubic phase transition, spontaneous polarization (its polarised direction is along c-axis direction) occurs, and from paraelectric phase ferroelectricity is changed into Phase, so as to excellent ferroelectricity and piezoelectric property.BaTiO3The features such as also there are high-k, good insulating properties, It has been used to prepare the electronic devices and components such as multilayer ceramic capacitor (MLCC), dynamic RAM (DRAM), node amplifier. BaTiO3As a kind of Typical dielectric materials, absorbed by the electronic polarization to medium, ionic polarization or interfacial polarization, decayed Electromagnetic wave, is also a kind of microwave absorbing material of great potential.In addition, BaTiO3Or a kind of typical piezoelectric, can Realize that acoustic vibration signal and electric signal are delicately changed.Therefore, BaTiO3Ceramics as the transmitting of underwater acoustic transducer and can connect Device is received, underwater navigation positioning, supersonic sounding and locating fish etc. is carried out and is done industry.
BaTiO3The consistency of ceramics is the key factor for affecting its piezoelectric property.For ceramic material, sintering temperature Improve, the prolongation of temperature retention time is conducive to it to realize densification；But the crystallite dimension that can cause material increases (make dielectric therewith The Key Performance Indicators such as constant are uncontrollable), meanwhile, high temperature sintering will bring great cost loss, constrain it industrially Batch production.As a rule, 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. sinters (SPS) work using discharge plasma Skill, is prepared for BaTiO of the consistency more than 99% under 1000 DEG C of sintering temperatures3Ceramics.Hiofumi et al. adopts 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 quick burning Knot (FS) technique, 5min is incubated at 1300 DEG C and is prepared for consistency for 97.2%BaTiO3Ceramics.X.-H.Wang et al. adopts two Step sintering (TSS) technique, two-step sintering minimum temperature is respectively under conditions of 950 DEG C and 900 DEG C, and consistency has finally been obtained 98.0% BaTiO3Ceramics.As can be seen here, 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.
The content of the invention
It is an object of the invention to provide a kind of process is simple, environmental friendliness, energy consumption are extremely low, the BaTiO of preparation3Ferroelectricity is made pottery Porcelain has the low temperature cold sintering preparation method of the barium titanate ferroelectric ceramicses of excellent dielectric properties and toughness.
The object of the present invention is achieved like this：
1. by Ba (OH)2And TiO2According to mol ratio 1.2:1 ratio is dissolved in deionized water, and ultrasonic disperse simultaneously stirs 20- 40min, is obtained Ba (OH)2Concentration is the Ba (OH) of 0.1mol/L2/TiO2Suspension；
2. by BaTiO3Nanometer grade powder and BaTiO3Sub-micron powder is according to mass ratio 1:1 ratio is mixed to get mixed Powder is closed, according still further to the Ba (OH) prepared by mixed-powder and step 12/TiO2The mass ratio of suspension is 4:1 ratio is added Suspension, grinds 0.5-1h in mortar；
3. by the BaTiO after grinding in step 23Mixed slurry is poured in mould, in room temperature environment, electrical heating forcing press On colded pressing, pressure be 450-500MPa, the dwell time be 10-20min；Hereafter, keep pressure constant, by heating-up temperature liter Up to 180-200 DEG C, heating rate 5-10 DEG C/min, temperature retention time is 3h；Prepared BaTiO3The preform blank of ceramics；
4.BaTiO3Ceramics preparative base substrate dries 12-18h at 200 DEG C；
5. by dried BaTiO3Ceramics preparative base substrate is sintered at 850-950 DEG C, and the BaTiO of high-compactness is obtained3 Ferroelectric ceramics.
The present invention can also include：
1st, 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.
2nd, the sintering is hot pressed sintering, and sintering temperature is 800-900 DEG C, and pressuring method is unidirectional or Bidirectional-pressure, applies 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.
3rd, the sintering is HIP sintering, and sintering temperature is 750-850 DEG C, and pressure is 50-100MPa, sintered heat insulating Time is 3-4h, and heating rate is 5 DEG C/min.
4th, the BaTiO3Purity ＞ 99.5% of nanometer grade powder, average grain diameter is 40-60nm, Emission in Cubic；It is described BaTiO3Purity ＞ 99.5% of sub-micron powder, average grain diameter is 400-600nm, Emission in Cubic.
For BaTiO3Ferroelectric ceramics sintering temperature is high, densification relatively difficult to achieve problem, and the present 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, under the calcined temperature less than 200 DEG C BaTiO is obtained3The preform blank of ceramics；Subsequently, in extremely low sintering The BaTiO of densification is prepared at temperature (≤950 DEG C)3Ceramic (consistency ＞ 97.5%)；The BaTiO of preparation3Ferroelectric ceramics has Excellent dielectric properties and toughness.The method process is simple, environmental friendliness, energy consumption are extremely low, can become underwater acoustic transducer Use BaTiO3The preferable preparation method of ferroelectric ceramics, with wide commercial application prospect.
BaTiO3The frequency range of ferroelectric ceramics dielectric properties test：1kHz-1MHz；Temperature range：25-100℃.According to GB/T4742-1984, test b aTiO3The toughness of ferroelectric ceramics.Jing is tested, and is burnt using low temperature cold proposed by the present invention BaTiO prepared by knot technique3Ferroelectric ceramics has excellent dielectric properties and fracture toughness, it is adaptable to manufacture underwater acoustic transducer Core component.
Specific embodiment
The low temperature cold sintering preparation method of the underwater acoustic transducer barium titanate ferroelectric ceramicses of the present invention, in low temperature presintering rank Section, under the evaporation of high pressure, water or the 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), you can prepare the barium titanate ferroelectric ceramicses of consistency higher (＞ 97.5%), Core component suitable for manufacturing underwater acoustic transducer.Illustrate below and the present invention is described in more detail.
Embodiment 1：
By Ba (OH)2And TiO2Powder is according to according to mol ratio 1.2:1 ratio inserts solvent (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 20-40min, and suspension of the concentration of Ba (OH) 2 for 0.1mol/L is obtained.
It is 99.5% to choose purity respectively, 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, calculates institute The quality of BaTiO3 powder is needed, by BaTiO3 nanometer grade powders and BaTiO3 sub-micron powders according to mass ratio 1:1 ratio, Add Ba (OH) 2/TiO2 suspension prepared in 25wt.% steps 1 that 0.5-1h is ground in mortar.
Room temperature is colded pressing after 10min, insulation and pressurize 3h at 180 DEG C, and pressure is 450MPa.By BaTiO3Ceramics preparative green bodies 12h is dried at a temperature of 200 DEG C.
Dried BaTiO3 ceramics preparatives base substrate is carried out into pressureless sintering, technological parameter is：850 DEG C of sintering temperature, protects Warm time 4h, vacuum is 1.3 × 10-2Pa。
Prepared BaTiO3Up to 97.8%, the toughness under room temperature is 6.24kJ/m to the consistency of ceramics2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency is respectively 1267,1218, 1180 and 1133；Dielectric loss is respectively 0.025,0.027,0.020 and 0.018.With the rising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increases therewith, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant during 10kHz, 100kH and 1MH frequency is respectively 1497,1434,1367 and 1316；Dielectric loss is respectively 0.034th, 0.035,0.025 and 0.021.
Embodiment 2：
By Ba (OH)2And TiO2Powder is according to according to mol ratio 1.2:1 ratio inserts solvent (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 30min, and Ba (OH) is obtained2Concentration is the suspension of 0.1mol/L.
It is 99.8% to choose purity respectively, 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 of BaTiO3 powder is needed, by BaTiO3 nanometer grade powders and BaTiO3 sub-micron powders according to mass ratio 1:1 ratio, Add Ba (OH) 2/TiO2 suspension prepared in 25wt.% steps 1 that 0.5-1h is ground in mortar.
Room temperature is colded pressing after 15min, insulation and pressurize 3h at 200 DEG C, and pressure is 500MPa.By BaTiO3Ceramics preparative green bodies 18h is dried at a temperature of 200 DEG C.
Vacuum non-pressure sintering is carried out, technological parameter is：900 DEG C of sintering temperature, temperature retention time 3h, vacuum is 1.3 × 10- 2Pa。
Prepared BaTiO3Up to 98.0%, the toughness under room temperature is 6.53kJ/m to the consistency of ceramics2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency is respectively 1760,1720, 1682 and 1637；Dielectric loss is respectively 0.019,0.027,0.018 and 0.015.With the rising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increases therewith, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant during 10kHz, 100kH and 1MH frequency is respectively 2057,1928,1798 and 1630；Dielectric loss is respectively 0.028th, 0.027,0.025 and 0.017.
Embodiment 3：
By Ba (OH)2And TiO2Powder is according to according to mol ratio 1.2:1 ratio inserts solvent (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 40min, and Ba (OH) is obtained2Concentration is the suspension of 0.1mol/L.
It is 99.99% to choose purity respectively, 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 of BaTiO3 powder is needed, by BaTiO3 nanometer grade powders and BaTiO3 sub-micron powders according to mass ratio 1:1 ratio, Add Ba (OH) 2/TiO2 suspension prepared in 25wt.% steps 1 that 0.5-1h is ground in mortar.
Room temperature is colded pressing after 20min, insulation and pressurize 3h at 200 DEG C, and pressure is 450MPa.By BaTiO3Ceramics preparative green bodies 12h is dried at a temperature of 200 DEG C.
Pressureless sintering is carried out, technological parameter is：950 DEG C of sintering temperature, temperature retention time 3h, argon gas protection.
Prepared BaTiO3Up to 98.4%, the toughness under room temperature is 6.71kJ/m to the consistency of ceramics2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency is respectively 2243,2215, 2170 and 3132；Dielectric loss is respectively 0.017,0.025,0.016 and 0.014.With the rising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increases therewith, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant during 10kHz, 100kH and 1MH frequency is respectively 2576,2365,2219 and 1940；Dielectric loss is respectively 0.026th, 0.025,0.023 and 0.016.
Embodiment 4：
By Ba (OH)2And TiO2Powder is according to according to mol ratio 1.2:1 ratio inserts solvent (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 30min, and Ba (OH) is obtained2Concentration is the suspension of 0.1mol/L.
It is 99.7% to choose purity respectively, 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 of BaTiO3 powder is needed, by BaTiO3 nanometer grade powders and BaTiO3 sub-micron powders according to mass ratio 1:1 ratio, Add Ba (OH) 2/TiO2 suspension prepared in 25wt.% steps 1 that 0.5-1h is ground in mortar.
Room temperature is colded pressing after 15min, insulation and pressurize 3h at 180 DEG C, and pressure is 450MPa.By BaTiO3Ceramics preparative green bodies 12h is dried at a temperature of 200 DEG C.
Vacuum heating-press sintering is carried out, technological parameter is：800 DEG C of sintering temperature, temperature retention time 4h, pressure is 50MPa, vacuum Spend for 1.3 × 10-2Pa。
Prepared BaTiO3Up to 97.9%, the toughness under room temperature is 6.46kJ/m to the consistency of ceramics2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency is respectively 1270,1221, 1189 and 1142；Dielectric loss is respectively 0.025,0.027,0.019 and 0.018.With the rising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increases therewith, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant during 10kHz, 100kH and 1MH frequency is respectively 1501,1438,1372 and 1325；Dielectric loss is respectively 0.033rd, 0.035,0.026 and 0.022.
Embodiment 5：
By Ba (OH)2And TiO2Powder is according to according to mol ratio 1.2:1 ratio inserts solvent (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 40min, and Ba (OH) is obtained2Concentration is the suspension of 0.1mol/L.
It is 99.9% to choose purity respectively, 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 of BaTiO3 powder is needed, by BaTiO3 nanometer grade powders and BaTiO3 sub-micron powders according to mass ratio 1:1 ratio, Add Ba (OH) 2/TiO2 suspension prepared in 25wt.% steps 1 that 0.5-1h is ground in mortar.
Room temperature is colded pressing after 20min, insulation and pressurize 3h at 190 DEG C, and pressure is 400MPa.By BaTiO3Ceramics preparative green bodies 18h is dried at a temperature of 200 DEG C.
Vacuum heating-press sintering is carried out, technological parameter is：850 DEG C of sintering temperature, temperature retention time 3h, pressure is 40MPa, vacuum Spend for 1.3 × 10-2Pa。
Prepared BaTiO3Up to 98.1%, the toughness under room temperature is 6.64kJ/m to the consistency of ceramics2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency is respectively 1762,1723, 1685 and 1641；Dielectric loss is respectively 0.018,0.026,0.017 and 0.015.With the rising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increases therewith, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant during 10kHz, 100kH and 1MH frequency is respectively 2060,1931,1800 and 1635；Dielectric loss is respectively 0.027th, 0.027,0.024 and 0.017.
Embodiment 6：
By Ba (OH)2And TiO2Powder is according to according to mol ratio 1.2:1 ratio inserts solvent (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 20min, and Ba (OH) is obtained2Concentration is the suspension of 0.1mol/L.
It is 99.99% to choose purity respectively, 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 of BaTiO3 powder is needed, by BaTiO3 nanometer grade powders and BaTiO3 sub-micron powders according to mass ratio 1:1 ratio, Add Ba (OH) 2/TiO2 suspension prepared in 25wt.% steps 1 that 0.5-1h is ground in mortar.
Room temperature is colded pressing after 20min, insulation and pressurize 3h at 180 DEG C, and pressure is 450MPa.By BaTiO3Ceramics preparative green bodies 18h is dried at a temperature of 200 DEG C.
Hot pressed sintering is carried out, technological parameter is：900 DEG C of sintering temperature, temperature retention time 3h, pressure is 30MPa, and argon gas is protected Shield.
Prepared BaTiO3Up to 98.4%, the toughness under room temperature is 6.75kJ/m to the consistency of ceramics2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency is respectively 2240,2215, 2166 and 3137；Dielectric loss is respectively 0.017,0.026,0.017 and 0.014.With the rising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increases therewith, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant during 10kHz, 100kH and 1MH frequency is respectively 2574,2369,2234 and 1947；Dielectric loss is respectively 0.025th, 0.026,0.023 and 0.015.
Embodiment 7：
By Ba (OH)2And TiO2Powder is according to according to mol ratio 1.2:1 ratio inserts solvent (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 20min, and Ba (OH) is obtained2Concentration is the suspension of 0.1mol/L.
It is 99.8% to choose purity respectively, 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 of BaTiO3 powder is needed, by BaTiO3 nanometer grade powders and BaTiO3 sub-micron powders according to mass ratio 1:1 ratio, Add Ba (OH) 2/TiO2 suspension prepared in 25wt.% steps 1 that 0.5-1h is ground in mortar.
Room temperature is colded pressing after 15min, insulation and pressurize 3h at 200 DEG C, and pressure is 500MPa.By BaTiO3Ceramics preparative green bodies 12h is dried at a temperature of 200 DEG C.
Vacuum HIP sintering is carried out, technological parameter is：800 DEG C of sintering temperature, temperature retention time 3h, pressure is 50MPa, Vacuum is 1.3 × 10-2Pa。
Prepared BaTiO3Up to 98.2%, the toughness under room temperature is 6.69kJ/m to the consistency of ceramics2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency is respectively 1870,1834, 1802 and 1781；Dielectric loss is respectively 0.017,0.026,0.016 and 0.015.With the rising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increases therewith, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant during 10kHz, 100kH and 1MH frequency is respectively 2182,2125,1907 and 1762；Dielectric loss is respectively 0.026th, 0.028,0.025 and 0.018.
Embodiment 8：
By Ba (OH)2And TiO2Powder is according to according to mol ratio 1.2:1 ratio inserts solvent (solvent is deionized water) In, ultrasonic disperse simultaneously stirs 20min, and Ba (OH) is obtained2Concentration is the suspension of 0.1mol/L.
It is 99.99% to choose purity respectively, 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 of BaTiO3 powder is needed, by BaTiO3 nanometer grade powders and BaTiO3 sub-micron powders according to mass ratio 1:1 ratio, Add Ba (OH) 2/TiO2 suspension prepared in 25wt.% steps 1 that 0.5-1h is ground in mortar.
Room temperature is colded pressing after 20min, insulation and pressurize 3h at 200 DEG C, and pressure is 450MPa.By BaTiO3Ceramics preparative green bodies 18h is dried at a temperature of 200 DEG C.
Vacuum HIP sintering is carried out, technological parameter is：850 DEG C of sintering temperature, temperature retention time 3h, pressure is 80MPa, Vacuum is 1.3 × 10-2Pa。
Prepared BaTiO3Up to 98.5%, the toughness under room temperature is 6.84kJ/m to the consistency of ceramics2.Room temperature (25 DEG C) under, BaTiO3Dielectric constant of the ferroelectric ceramics in 1kHz, 10kHz, 100kH and 1MH frequency is respectively 2354,2330, 2297 and 3254；Dielectric loss is respectively 0.018,0.026,0.017 and 0.015.With the rising of test temperature, BaTiO3Pottery The dielectric constant and dielectric loss of porcelain also increases therewith, when test temperature is 100 DEG C, BaTiO3Ferroelectric ceramics 1kHz, Dielectric constant during 10kHz, 100kH and 1MH frequency is respectively 2695,2486,2340 and 2062；Dielectric loss is respectively 0.025th, 0.026,0.022 and 0.017.

Claims (5)

1. a kind of low temperature cold sintering preparation method of barium titanate ferroelectric ceramicses, is characterized in that：
Step 1. is by Ba (OH)2And TiO2According to mol ratio 1.2:1 ratio is dissolved in deionized water, and ultrasonic disperse simultaneously stirs 20- 40min, is obtained Ba (OH)2Concentration is the Ba (OH) of 0.1mol/L2/TiO2Suspension；
Step 2. is by BaTiO3Nanometer grade powder and BaTiO3Sub-micron powder is according to mass ratio 1:1 ratio is mixed to get mixed Powder is closed, according still further to the Ba (OH) prepared by mixed-powder and step 12/TiO2The mass ratio of suspension is 4:1 ratio is added Suspension, grinds 0.5-1h in mortar；
Step 3. by step 2 grind after BaTiO3Mixed slurry is poured in mould, in room temperature environment, electrical heating forcing press On colded pressing, pressure be 450-500MPa, the dwell time be 10-20min；Hereafter, keep pressure constant, by heating-up temperature liter Up to 180-200 DEG C, heating rate 5-10 DEG C/min, temperature retention time is 3h；Prepared BaTiO3The preform blank of ceramics；
Step 4.BaTiO3Ceramics preparative base substrate dries 12-18h at 200 DEG C；
Step 5. is by dried BaTiO3Ceramics preparative base substrate is sintered at 850-950 DEG C, and the BaTiO of high-compactness is obtained3 Ferroelectric ceramics.
2. the low temperature cold sintering preparation method of barium titanate ferroelectric ceramicses according to claim 1, is characterized in that：The sintering It is pressureless sintering, sintering temperature is 850-950 DEG C, the sintered heat insulating time is 3-4h, 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 ceramicses according to claim 1, is characterized in that：The sintering It is hot pressed sintering, sintering temperature is 800-900 DEG C, pressuring method is unidirectional or Bidirectional-pressure, applying pressure is 30-50MPa, is burnt Knot temperature retention 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 ceramicses according to claim 1, is characterized in that：The sintering It is HIP sintering, sintering temperature is 750-850 DEG C, pressure is 50-100MPa, the sintered heat insulating time is 3-4h, and heat up speed Rate is 5 DEG C/min.
5. the low temperature cold sintering preparation method of the barium titanate ferroelectric ceramicses according to Claims 1-4 any one, its feature It is：The BaTiO3Purity ＞ 99.5% of nanometer grade powder, average grain diameter is 40-60nm, Emission in Cubic；The BaTiO3Sub-micro Purity ＞ 99.5% of nanoscale powder, average grain diameter is 400-600nm, Emission in Cubic.
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CN110041069A (en) * 2019-05-31 2019-07-23 河南科技大学 A kind of microwave dielectric ceramic materials and preparation method thereof
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CN117303889A (en) * 2023-09-21 2023-12-29 京瓷高压(北京)科技有限公司 Cold-sintered barium strontium titanate-based ceramic and preparation method thereof

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