CN111762810A - Preparation method of tetragonal phase nano barium titanate - Google Patents
Preparation method of tetragonal phase nano barium titanate Download PDFInfo
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- CN111762810A CN111762810A CN202010683854.XA CN202010683854A CN111762810A CN 111762810 A CN111762810 A CN 111762810A CN 202010683854 A CN202010683854 A CN 202010683854A CN 111762810 A CN111762810 A CN 111762810A
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- titanium dioxide
- barium titanate
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- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 79
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052788 barium Inorganic materials 0.000 claims abstract description 13
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- XBYNNYGGLWJASC-UHFFFAOYSA-N barium titanium Chemical compound [Ti].[Ba] XBYNNYGGLWJASC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011268 mixed slurry Substances 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 238000004137 mechanical activation Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 claims description 6
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical group [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 10
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 7
- 239000000919 ceramic Substances 0.000 abstract description 4
- 239000010419 fine particle Substances 0.000 abstract description 3
- WNKMTAQXMLAYHX-UHFFFAOYSA-N barium(2+);dioxido(oxo)titanium Chemical compound [Ba+2].[O-][Ti]([O-])=O WNKMTAQXMLAYHX-UHFFFAOYSA-N 0.000 description 75
- 239000012071 phase Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 238000002441 X-ray diffraction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000001994 activation Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009643 growth defect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
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Abstract
The invention belongs to the technical field of electronic ceramic powder materials, and particularly relates to a preparation method of tetragonal phase nano barium titanate. The invention provides a preparation method of tetragonal phase nano barium titanate, which comprises the following steps: mechanically activating titanium dioxide in absolute ethyl alcohol to obtain activated titanium dioxide slurry; mixing the activated titanium dioxide slurry with a soluble barium source, and adding a mineralizer into the obtained barium-titanium mixed slurry under the condition of protective gas atmosphere to obtain a mixture to be reacted; and preheating the mixture to be reacted, and then heating to perform hydrothermal reaction to obtain the tetragonal-phase nano barium titanate. The test results of the embodiment show that the tetragonal-phase nano barium titanate prepared by the preparation method provided by the invention has regular microscopic morphology, uniform particle size, fine particles, good dispersibility, excellent crystallization performance and high tetragonal phase.
Description
Technical Field
The invention belongs to the technical field of electronic ceramic powder materials, and particularly relates to a preparation method of tetragonal phase nano barium titanate.
Background
Barium titanate (BaTiO)3) Because of having higher dielectric constant, excellent ferroelectric, piezoelectric and insulating properties, it is considered as the base material of ceramic electronic components and is known as the pillar of electronic ceramic industry. Barium titanate-based materials are currently widely used to fabricate multilayer ceramic capacitors (MLCCs). With the rapid development of electronic and other communication devices, MLCCs are gradually miniaturized and have large capacity, which requires further realization of thinning of media and multilayering of lamination in terms of process, and barium titanate powder with high-quality crystal form, ultra-fine and uniform particle size is one of the keys for realizing the MLCC devices.
In the prior art, titanium tetrachloride is used as a titanium source to prepare nano barium titanate powder, and titanium hydroxide with high specific area generated by hydrolysis of titanium tetrachloride exists on the surface of the nano barium titanate powder, and pores and poor crystallization quality appear on the surface of the barium titanate powder due to the loose and porous titanium hydroxide with high specific area; the nano barium titanate powder crystal prepared by adopting titanium oxide as a titanium source is irregular, the crystal form quality is low, and the particles are distributed unevenly (Chinese patent CN 104828858A). In the above methods, the barium titanate is industrially produced by either a solid-phase method or a hydrothermal method, but the defects of non-uniform particle distribution, low tetragonal phase ratio below 200nm, poor crystallization quality and the like still exist, and the requirements of high performance and miniaturization of modern electronic components cannot be met.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing tetragonal nano barium titanate, wherein the tetragonal nano barium titanate obtained by the preparation method provided by the present invention has characteristics of uniform particle size distribution, small particle size and high crystallization quality.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a preparation method of tetragonal phase nano barium titanate, which comprises the following steps:
mechanically activating titanium dioxide in absolute ethyl alcohol to obtain activated titanium dioxide slurry;
mixing the activated titanium dioxide slurry with a soluble barium source, and adding a mineralizer into the obtained barium-titanium mixed slurry under the condition of protective gas atmosphere to obtain a mixture to be reacted;
and preheating the mixture to be reacted, and then heating to perform hydrothermal reaction to obtain the tetragonal-phase nano barium titanate.
Preferably, the solid content of the activated titanium dioxide slurry is 8-16%.
Preferably, the mechanical activation mode is ball milling; the grinding ball for ball milling is a zirconium ball; the diameter of the zirconium ball is 0.1-0.4 mm; the ball-milling material-ball ratio is (3-5): 1; the rotation speed of the ball milling is 12.1-12.8 m/s, and the time is 4-7 h.
Preferably, the feeding rate of the mechanical activation is 7-70 kg/h.
Preferably, the soluble barium source is barium hydroxide, barium hydroxide octahydrate, barium nitrate or barium chloride.
Preferably, the molar ratio of the activated titanium dioxide, the soluble barium source and the mineralizer in the activated titanium dioxide slurry is (15-20): (15-30): (0.8 to 1).
Preferably, the pH value of the mixture to be reacted is more than or equal to 13.
Preferably, the preheating temperature is 80-100 ℃, and the time is 1.5-3. h.
Preferably, the temperature rise rate is 5-8 ℃/min.
Preferably, the temperature of the hydrothermal reaction is 180-250 ℃ and the time is 36-72 h.
The invention provides a preparation method of tetragonal phase nano barium titanate, which comprises the following steps: mechanically activating titanium dioxide in absolute ethyl alcohol to obtain activated titanium dioxide slurry; mixing the activated titanium dioxide slurry with a soluble barium source, and adding a mineralizer into the obtained reaction system under the condition of protective gas atmosphere to obtain a mixture to be reacted; and preheating the mixture to be reacted, and then heating to perform hydrothermal reaction to obtain the tetragonal-phase nano barium titanate. The preparation method provided by the invention comprises the following steps of firstly, carrying out mechanical activation treatment on titanium dioxide in absolute ethyl alcohol, so that large titanium dioxide particles which are seriously agglomerated originally are changed into small titanium dioxide particles with uniform particle size, and the small titanium dioxide particles can be stably dispersed in an ethanol solution for a long time; in addition, anhydrous ethanol is selected as a disperse phase in the titanium dioxide in mechanical activation, so that the titanium dioxide can be uniformly dispersed in a dispersion liquid system for a long time without agglomeration and precipitation, titanium dioxide slurry after mechanical activation is used as a titanium source, has a high specific surface area, and simultaneously weakens a hydroxylation steric hindrance effect which is not beneficial to a mass transfer process, explosive nucleation which is beneficial to reaction is carried out in the process of preparing barium titanate, the particle size of the generated barium titanate powder is reduced, and the particle size distribution concentration degree is improved; according to the invention, activated titanium dioxide slurry which is obtained by activation and is high in dispersion, uniform in particle distribution and not easy to settle and barium hydroxide are subjected to hydrothermal treatment under the action of a mineralizer, on the basis of mechanical activation of titanium dioxide, the uniformity of titanium source particles is controlled, the reaction activity is increased, the preparation of tetragonal phase nano barium titanate is realized, and the obtained tetragonal phase nano barium titanate is small and uniform in particle size and has no crystal growth defects.
Further, under the mechanical activation condition provided by the invention, the activated titanium dioxide slurry of the activated titanium dioxide particles with the particle size of 60-200 nm and uniform distribution can be obtained, the sufficient degree of material contact in a hydrothermal reaction system can be increased, the mass transfer can be more efficient in the process of preparing barium titanate, and the tetragonal phase nano barium titanate with small and uniform particles and high crystallization quality can be obtained.
The test results of the embodiment show that the tetragonal-phase nano barium titanate prepared by the preparation method provided by the invention has regular microscopic morphology, uniform particle size, fine particles, good dispersibility, excellent crystallization performance and high tetragonal phase.
Drawings
FIG. 1 is an SEM image of tetragonal nano barium titanate prepared in example 1;
FIG. 2 is an XRD pattern of tetragonal nano barium titanate prepared in example 1;
FIG. 3 is an SEM photograph of barium titanate prepared in comparative example 1;
FIG. 4 is an XRD pattern of barium titanate prepared in comparative example 1;
FIG. 5 is a FT-IR chart of titania slurries prepared in example 1, example 4 and comparative example 1;
FIG. 6 is an SEM photograph of tetragonal nano barium titanate prepared in example 2;
fig. 7 is an XRD pattern of tetragonal nano barium titanate prepared in example 2;
FIG. 8 is an SEM photograph of barium titanate prepared in comparative example 2;
FIG. 9 is an XRD pattern of barium titanate prepared in comparative example 2;
FIG. 10 is an SEM image of tetragonal nano barium titanate prepared in example 3;
fig. 11 is an XRD pattern of tetragonal nano barium titanate prepared in example 3;
FIG. 12 is an SEM photograph of barium titanate prepared in comparative example 3;
fig. 13 is an XRD pattern of barium titanate prepared in comparative example 3.
Detailed Description
The invention provides a preparation method of tetragonal phase nano barium titanate, which comprises the following steps:
mechanically activating titanium dioxide in absolute ethyl alcohol to obtain activated titanium dioxide slurry;
mixing the activated titanium dioxide slurry with a soluble barium source, and adding a mineralizer into the obtained barium-titanium mixed slurry under the condition of protective gas atmosphere to obtain a mixture to be reacted;
and preheating the mixture to be reacted, and then heating to perform hydrothermal reaction to obtain the tetragonal-phase nano barium titanate.
In the present invention, unless otherwise specified, each component in the preparation method is a commercially available product well known to those skilled in the art.
The invention mechanically activates titanium dioxide in ethanol water solution to obtain activated titanium dioxide slurry.
In the present invention, the titanium dioxide is preferably titanium dioxide powder; the particle size of the titanium dioxide powder is preferably 5-50 nm, and more preferably 10-45 nm. In the invention, the solid content of the activated titanium dioxide slurry is preferably 8-16%, and more preferably 8-12%.
In the present invention, the mechanical activation is preferably performed by ball milling. In the invention, the grinding balls of the ball milling are preferably zirconium balls; the diameter of the zirconium ball is preferably 0.1-0.4 mm, and more preferably 0.15-0.35 mm. The invention has no special limitation on the grading of the zirconium balls, and any grading can be adopted. In the invention, the ball-milling material ball ratio is preferably (3-5): 1, more preferably (3.5 to 4.5): 1. in the invention, the rotation speed of the ball milling is preferably 12.1-12.8 m/s, and more preferably 12.3-12.6 m/s; the time is preferably 4 to 7 hours, and more preferably 4.5 to 6.5 hours.
In the present invention, the feeding rate of the mechanical activation is preferably 7 to 70kg/h, more preferably 15 to 60 kg/h.
After the activated titanium dioxide slurry is obtained, the activated titanium dioxide slurry is mixed with a soluble barium source to obtain barium-titanium mixed slurry.
In the present invention, the apparatus for performing the remaining steps except for the mechanical activation of the titanium dioxide is preferably a hydrothermal kettle; the material of the inner container of the hydrothermal kettle is preferably para-polyphenol (PPL).
In the present invention, the soluble barium source is preferably barium hydroxide, barium hydroxide octahydrate, barium nitrate or barium chloride.
After the barium-titanium mixed slurry is obtained, a mineralizer is added into the barium-titanium mixed slurry under the condition of protective gas atmosphere, and a mixture to be reacted is obtained.
In the present invention, the protective gas is preferably nitrogen.
In the present invention, the method for obtaining the protective gas atmosphere preferably comprises the steps of: and introducing protective gas into the barium-titanium mixed slurry under the condition of stirring. In the present invention, the stirring rate is preferably 200 to 400rpm, and more preferably 250 to 350 rpm. In the invention, the flow rate of the introduced protective gas is preferably 6-18L/min, and more preferably 10-16L/min. In the invention, the introducing time of the protective gas is preferably 0.5-2 h, and more preferably 1-1.7 h. In the present invention, the purity of the introduced protective gas is preferably 99.9% or more.
In the present invention, the mineralizer is preferably ammonia, sodium hydroxide, or potassium hydroxide. In the invention, the mass percentage concentration of the ammonia water is preferably 25-28%, and more preferably 26-27%. In the present invention, the sodium hydroxide and potassium hydroxide are preferably provided in the form of a solid or a solution; when the sodium hydroxide or potassium hydroxide is a solution, the concentration of the sodium hydroxide solution and the potassium hydroxide solution is not particularly limited in the present invention.
In the present invention, the molar ratio of the activated titanium dioxide, the soluble barium source and the mineralizer in the activated titanium dioxide slurry is preferably (15 to 20): (15-30): (0.8-1), more preferably (15-17): (20-30): (0.85 to 1), most preferably 15: 30: 1. in the present invention, the pH of the mixture to be reacted is preferably not less than 13.
In the invention, the filling degree of the mixture to be reacted in the hydrothermal kettle is preferably 60-80%.
After the mixture to be reacted is obtained, the mixture to be reacted is preheated and then heated for hydrothermal reaction, and the tetragonal phase nano barium titanate is obtained.
In the invention, the preheating temperature is preferably 80-100 ℃, and more preferably 90-100 ℃; the time is preferably 1.5 to 3.h, and more preferably 1.5 to 2 h. In the present invention, the preheating facilitates complete dissolution of the soluble barium source, promoting the occurrence of the explosive nucleation reaction of barium titanate.
In the invention, the heating rate is preferably 5-8 ℃/min, and more preferably 5.5-7.5 ℃/min. The invention is beneficial to barium titanate explosive nucleation in a short time by controlling the heating rate.
In the invention, the temperature of the hydrothermal reaction is preferably 180-250 ℃, and more preferably 200-250 ℃; the time is preferably 36 to 72 hours, and more preferably 36 to 48 hours.
After the hydrothermal reaction, the method preferably further comprises the steps of sequentially carrying out solid-liquid separation and washing on the hydrothermal reaction product, wherein in the method, the solid-liquid separation is preferably filtration or centrifugation. In the present invention, the washing is preferably water washing, and the washing method of the present invention is not particularly limited, and is based on the fact that impurities on the surface of the solid obtained by solid-liquid separation can be removed. In the present invention, when the conductivity of water in the washing waste liquid obtained after the washing is not more than 2. mu.s/cm, the washing is considered to be completed.
In order to further illustrate the present invention, the following examples are provided to describe the preparation method of the tetragonal nano barium titanate of the present invention in detail, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing 12g of titanium dioxide and 150mL of absolute ethyl alcohol, and carrying out ball milling activation, wherein the ball milling activation conditions are as follows: selecting zirconium beads with the diameter of 0.1mm, wherein the ratio of the material to the balls is 3: 1. the rotating speed is 12.1m/s, the feeding rate is 13kg/h, and the mechanical activation time is 4.75h, so that the activated titanium dioxide slurry with the solid content of 9.2 percent is obtained;
mixing 150mL of the activated titanium dioxide slurry with 95g of barium hydroxide octahydrate, introducing nitrogen for 30min under the conditions of stirring speed of 300rpm and flow rate of 10L/min, and then adding 150mL of ammonia water with the mass percentage of 28% into the obtained reaction system to obtain a mixture to be reacted;
preheating the mixture to be reacted for 1.5h at the temperature of 100 ℃, then heating to 180 ℃ at the heating rate of 8 ℃/min, carrying out hydrothermal reaction for 36h, filtering and washing to obtain the tetragonal-phase nano barium titanate.
Comparative example 1
The remaining preparation method was the same as in example 1 without mechanical activation of titanium dioxide, to obtain barium titanate.
Example 2
Mixing 12g of titanium dioxide and 150mL of absolute ethyl alcohol, and carrying out mechanical activation, wherein the mechanical activation conditions are as follows: selecting zirconium beads with the diameter of 0.1mm, wherein the ratio of the material to the balls is 3: 1. the rotating speed is 12.1m/s, the feeding rate is 13kg/h, and the mechanical activation time is 4.75h, so that the activated titanium dioxide slurry with the solid content of 9.2 percent is obtained;
mixing 150mL of the activated titanium dioxide slurry with 95g of barium hydroxide octahydrate, introducing nitrogen for 30min under the conditions of stirring speed of 250rpm and flow rate of 15L/min, and then adding 150mL of ammonia water with the mass percentage of 28% into the obtained reaction system to obtain a mixture to be reacted;
preheating the mixture to be reacted for 1.5h at the temperature of 100 ℃, then heating to 200 ℃ at the heating rate of 6 ℃/min, carrying out hydrothermal reaction for 36h, filtering and washing to obtain the tetragonal phase nano barium titanate.
Comparative example 2
No mechanical activation of the titanium dioxide was carried out, and the remaining preparation process was identical to that of example 2, to obtain barium titanate.
Example 3
Mixing 12g of titanium dioxide and 150mL of absolute ethyl alcohol, and carrying out mechanical activation, wherein the mechanical activation conditions are as follows: selecting zirconium beads with the diameter of 0.1mm, wherein the ratio of the material to the balls is 3: 1. the rotating speed is 12.1m/s, the feeding rate is 13kg/h, and the mechanical activation time is 4.75h, so that the activated titanium dioxide slurry with the solid content of 9.2 percent is obtained;
mixing 150mL of the activated titanium dioxide slurry with 95g of barium hydroxide octahydrate, introducing nitrogen for 30min under the conditions of stirring speed of 200rpm and flow rate of 15L/min, and then adding 150mL of ammonia water with the mass percentage of 28% into the obtained reaction system to obtain a mixture to be reacted;
preheating the mixture to be reacted for 1.5h at the temperature of 100 ℃, then heating to 250 ℃ at the heating rate of 5 ℃/min, carrying out hydrothermal reaction for 36h, filtering and washing to obtain the tetragonal-phase nano barium titanate.
Comparative example 3
No mechanical activation of the titanium dioxide was carried out, and the remaining preparation process was identical to that of example 3, to obtain barium titanate.
Scanning electron microscope tests and X-ray diffraction tests are carried out on the tetragonal nano barium titanate obtained in examples 1-3 and the barium titanate obtained in comparative examples 1-3, and the test charts are shown in figures 1-4 and figures 6-12, wherein figure 1 is an SEM (scanning electron microscope) chart of the tetragonal nano barium titanate prepared in example 1; FIG. 2 is an XRD pattern of tetragonal nano barium titanate prepared in example 1; FIG. 3 is an SEM photograph of barium titanate prepared in comparative example 1; FIG. 4 is an XRD pattern of barium titanate prepared in comparative example 1; FIG. 6 is an SEM photograph of tetragonal nano barium titanate prepared in example 2; fig. 7 is an XRD pattern of tetragonal nano barium titanate prepared in example 2; FIG. 8 is an SEM photograph of barium titanate prepared in comparative example 2; FIG. 9 is an XRD pattern of barium titanate prepared in comparative example 2; FIG. 10 is an SEM image of tetragonal nano barium titanate prepared in example 3; fig. 11 is an XRD pattern of tetragonal nano barium titanate prepared in example 3; FIG. 12 is an SEM photograph of barium titanate prepared in comparative example 3; fig. 13 is an XRD pattern of barium titanate prepared in comparative example 3.
As can be seen from fig. 1, 3, 6, 8, 10 and 12, the tetragonal nano barium titanate particles provided by the invention have more regular microscopic morphology, more uniform particle size, fine particles, good dispersibility and excellent surface crystal morphology; the barium titanate obtained by titanium dioxide-free mechanical activation has large and thick particles, poor uniformity and poor crystallization quality. Moreover, as can be seen from fig. 10, the tetragonal nano barium titanate crystal particles provided by the present invention have a c/a of 1.0082, and have a high tetragonal feature.
As can be seen from fig. 2, 4, 7, 9, 11 and 13, the preparation method containing the titanium dioxide mechanical activation process provided by the invention successfully prepares barium titanate without impurity peaks, and the obtained tetragonal phase nano barium titanate has high purity.
The particle size distributions of the tetragonal phase nano barium titanate obtained in examples 1 to 3 and the barium titanate obtained in comparative examples 1 to 3 were measured using a malvern laser particle size analyzer, the dispersion calculation formula is formula (1), and the obtained measurement results are shown in table 1.
Dispersion (D)90-D10)/D50Formula (1).
TABLE 1 results of particle size dispersion test of barium titanate obtained in examples 1 to 3 and comparative examples 1 to 3
| Dispersion of | Dispersion of | ||
| Example 1 | 1.01 | Comparative example 1 | 1.38 |
| Example 2 | 0.81 | Comparative example 2 | 1.41 |
| Example 3 | 0.83 | Comparative example 3 | 1.76 |
As can be seen from table 1, compared with the technical scheme of no mechanical activation of titanium dioxide, the tetragonal nano barium titanate obtained by the preparation method for mechanical activation of titanium dioxide provided by the invention has smaller dispersion, and the barium titanate crystal particles are more uniformly distributed.
Example 4
The mechanical activation time is 6.75h, and the rest steps are the same as those of the example 1, so that the tetragonal phase nano barium titanate is obtained.
Fourier Infrared Spectroscopy tests were performed on the titania slurries of example 1, example 4 and comparative example 1, and the FT-IR chart obtained is shown in FIG. 5. As can be seen from fig. 5, the stretching vibration of the hydroxyl group is clearly shown at the position with the wave number of 3400, when the mechanical activation process provided by the present invention is adopted, the transmittance of the mechanical activation process is respectively 28% and 49% when the mechanical activation process is used for 4.75h and 6.75h, and is correspondingly improved compared with the transmittance of the titanium oxide without mechanical activation process, which is 25%, thereby showing that the mechanical activation process provided by the present invention can significantly reduce the influence of barium titanate nucleation and growth caused by the hydroxyl group defect.
The results show that the tetragonal nano barium titanate prepared by the preparation method provided by the invention has the characteristics of high quality (crystallinity), high dispersion (uniform particle distribution), high tetragonal phase and high morphology regularity (tetragonal or spherical); the tetragonal phase nano barium titanate prepared by the preparation method can meet the preparation requirement of the miniaturization of the MLCC device, and simultaneously ensures the requirements of the MLCC device on high capacity, high volume efficiency, high dielectric constant and low dielectric loss.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of tetragonal phase nano barium titanate is characterized by comprising the following steps:
mechanically activating titanium dioxide in absolute ethyl alcohol to obtain activated titanium dioxide slurry;
mixing the activated titanium dioxide slurry with a soluble barium source, and adding a mineralizer into the obtained barium-titanium mixed slurry under the condition of protective gas atmosphere to obtain a mixture to be reacted;
and preheating the mixture to be reacted, and then heating to perform hydrothermal reaction to obtain the tetragonal-phase nano barium titanate.
2. The production method according to claim 1, wherein the solid content of the activated titanium dioxide slurry is 8 to 16%.
3. The method of claim 1, wherein the mechanical activation is by ball milling; the grinding ball for ball milling is a zirconium ball; the diameter of the zirconium ball is 0.1-0.4 mm; the ball-milling material-ball ratio is (3-5): 1; the rotation speed of the ball milling is 12.1-12.8 m/s, and the time is 4-7 h.
4. The method of claim 1 or 3, wherein the feeding rate of the mechanical activation is 7 to 70 kg/h.
5. The method of claim 1, wherein the soluble barium source is barium hydroxide, barium hydroxide octahydrate, barium nitrate, or barium chloride.
6. The preparation method according to claim 1, wherein the molar ratio of the activated titanium dioxide, the soluble barium source and the mineralizer in the activated titanium dioxide slurry is (15-20): (15-30): (0.8 to 1).
7. The method according to claim 1 or 6, wherein the pH of the mixture to be reacted is at least 13.
8. The preparation method according to claim 1, wherein the preheating temperature is 80-100 ℃ and the preheating time is 1.5-3.0 h.
9. The method according to claim 1, wherein the temperature is raised at a rate of 5 to 8 ℃/min.
10. The preparation method according to claim 1 or 9, wherein the hydrothermal reaction is carried out at a temperature of 180 to 250 ℃ for 36 to 72 hours.
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