WO2021168736A1 - Method for preparing tetragonal-phase barium titanate nanoparticle - Google Patents

Method for preparing tetragonal-phase barium titanate nanoparticle Download PDF

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WO2021168736A1
WO2021168736A1 PCT/CN2020/076963 CN2020076963W WO2021168736A1 WO 2021168736 A1 WO2021168736 A1 WO 2021168736A1 CN 2020076963 W CN2020076963 W CN 2020076963W WO 2021168736 A1 WO2021168736 A1 WO 2021168736A1
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barium
water
organosol
barium titanate
soluble salt
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PCT/CN2020/076963
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French (fr)
Chinese (zh)
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董岩
宁尚超
徐勤勤
詹子豪
刘安晗
魏默予
张东志
蒋建清
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东南大学
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Priority to CN202080093960.0A priority Critical patent/CN115135606B/en
Priority to JP2022548111A priority patent/JP7487971B2/en
Priority to PCT/CN2020/076963 priority patent/WO2021168736A1/en
Publication of WO2021168736A1 publication Critical patent/WO2021168736A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium

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  • the invention relates to a technology for preparing tetragonal phase barium titanate nanoparticles, and belongs to the technical field of electronic ceramic material preparation.
  • Barium titanate (BaTiO 3 ) has high dielectric constant and low dielectric loss, excellent ferroelectric, piezoelectric, voltage resistance and insulation properties. It is the basic matrix material of electronic ceramic components and is called the backbone of electronic ceramics. It is widely used in the manufacture of high-capacitance capacitors, multilayer substrates, various sensors, semiconductor materials and sensitive components. With the rapid development of electronic components in the direction of high integration, high precision and miniaturization, it is necessary to prepare nano-barium titanate with high dispersibility and high crystallinity. The research on the preparation technology of nano-barium titanate has always been electronic The research focus in the field of ceramic materials.
  • barium titanate powder is generally prepared by high-temperature solid-phase method, using titanium dioxide and barium carbonate powder as raw materials, and high-temperature calcination synthesis after mixing.
  • the synthesis temperature is often as high as 1400-1500°C.
  • the prepared barium titanate particles are coarse and have a large particle size. All are in the micron level.
  • the methods for preparing nano-barium titanate particles include chemical precipitation, sol-gel (Sol-Gel) and hydrothermal methods.
  • Chemical precipitation also includes direct precipitation, oxalate co-precipitation, citrate, and composite
  • Both the peroxide method and the alkoxide hydrolysis method first prepare precursors, such as hydroxides, oxalates, etc., and then calcinate and react to form barium titanate phase at high temperatures.
  • the sol-gel method is to prepare a gel containing titanium and barium. The gel is calcined and decomposed at a high temperature and synthesized by reaction to obtain a barium titanate phase.
  • the use of a high melting point water-soluble salt as the isolation phase can prevent the barium titanate precursor particles from agglomerating, and can prevent the barium titanate particles from sintering during the high-temperature calcination process, and it is easy to wash and remove after calcination, which is simple and convenient.
  • microemulsion coating salt shell method (Chinese patent CN201610365324.4), salt-containing sol precipitation method (Chinese patent CN201610699775.1), water-soluble sulfate co-precipitation method (Chinese patent CN201810037875.7), water-soluble salt Nanoparticle isolation method (Chinese patent CN201810037620.0) and metal acetylacetonate solution impregnation method (2019101041603) and other methods, but these processes are more complicated and it is difficult to synthesize pure phase barium titanate.
  • the present invention provides a method for rapidly synthesizing tetragonal barium titanate nanoparticles, which can prepare pure tetragonal barium titanate nanoparticles with a particle size of less than 100nm, uniform particle size, and good dispersibility on a large scale.
  • the technology has good application prospects in the field of electronic ceramics.
  • the method for preparing highly dispersed tetragonal barium titanate nanoparticles of the present invention includes the following steps:
  • the organic solvent is one of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol and propylene glycol;
  • the water-soluble salt coated with the dry gel film is calcined at a temperature above 600°C and below the melting point of the salt.
  • the dry gel film is converted into barium titanate nanoparticles, which are dispersed and attached to the surface of the water-soluble salt particles to form a calcined product;
  • the water-soluble salt in step 2) is potassium sulfate, sodium sulfate, potassium chloride or sodium chloride.
  • the molar concentration of titanium is between 0.01M and 1M, and the molar ratio of tetrabutyl titanate, barium acetate and barium compound is 1. :1:1-6.
  • the barium compound in the organosol containing titanium and barium in step 1), is barium acetate, barium hydroxide, barium nitrate or barium carbonate.
  • the present invention has the following advantages:
  • the use of high melting point water-soluble salt as the isolation phase can prevent the agglomeration and sintering of nanoparticles at high temperatures, and is easy to wash and remove after calcination, and the process is simple and convenient.
  • the project team has tried various methods such as molten salt isolation method, microemulsion coating salt shell method, salt-containing sol precipitation method, water-soluble sulfate co-precipitation method, water-soluble salt nanoparticle isolation method, and metal acetylacetonate solution impregnation method.
  • the present invention uses organosol containing titanium and barium to impregnate the water-soluble salt.
  • the organosol undergoes a sol-gel transition during the subsequent heat preservation process.
  • the organic solvent in the gel evaporates, the gel shrinks and can be completely dried.
  • a layer of dry gel film is coated on the surface of the water-soluble salt particles.
  • the organic matter in the dry gel film is calcined and decomposed to generate barium titanate nanoparticles, and the generated barium titanate nanoparticles are dispersed and attached
  • the salt is removed by washing with water after cooling, and barium titanate nanoparticles with good dispersibility and crystallinity can be obtained.
  • titanium ions and barium ions are combined through complexation, so pure tetragonal phase barium titanate can be synthesized above 600°C, which completely solves the problem of residual phases.
  • the invention utilizes the shrinkage characteristic of the gel when it is dried to form a uniform dry gel film on the surface of the water-soluble salt particles.
  • organic matter decomposes, and this dry gel film becomes barium titanate nanoparticles dispersed on the surface of the water-soluble salt particles.
  • Our research shows that these nanoparticles are closely attached to the surface of the salt particles, have a strong binding force with the water-soluble salt particles, and will not fall off the surface of the salt particles.
  • diffusion and mass transfer will not occur, and agglomeration and sintering will not occur.
  • the calcination temperature of the present invention is high (up to the melting point of potassium sulfate), so the nano-particles are perfectly crystallized, there are almost no crystal defects inside the particles, and there is no residual cubic barium titanate. Therefore, the present invention can obtain highly dispersed pure tetragonal barium titanate nanoparticles.
  • the present invention uses potassium sulfate (melting point 1067°C), sodium sulfate (melting point 884°C), sodium chloride (melting point 801°C), potassium chloride (melting point 770°C) these four water-soluble salts to prepare titanic acid Barium nanoparticles.
  • surfactants include polyethylene glycol, polyvinylpyrrolidone, carboxylic acid surfactants and the like.
  • the invention can quickly prepare pure tetragonal barium titanate nanoparticles with good dispersibility in batches, and solve the problems of agglomeration and sintering of the nanoparticles.
  • the metal salt containing La, Ce, Al, Mn, Nd and other elements is dissolved in the organosol of the present invention to realize the doping of barium titanate.
  • the preparation method of the invention is simple and easy to produce on a large scale.
  • Barium titanate nanoparticles prepared at 900° C. using the method of the present invention have a particle size of about 60-80 nm and good dispersibility.
  • Figure 2 shows the distribution of barium titanate nanoparticles on the surface of salt particles, and the barium titanate nanoparticles are dispersed.
  • Example 1 Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 2 Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and sodium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of sodium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 3 Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium chloride are mixed, and the excess organosol is discarded after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium chloride, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 4 Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol is mixed with sodium chloride, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of sodium chloride, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 5 Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.01M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 6 Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 7 Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:1.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 8 Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, in which the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:6.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 9 Dissolve tetrabutyl titanate in ethylene glycol ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium , Wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 10 Dissolve tetrabutyl titanate in ethylene glycol butyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 11 Dissolve tetrabutyl titanate in ethanol to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium, in which titanium The molar concentration of is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 75°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 12 Dissolve tetrabutyl titanate in n-propanol to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium,
  • the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 90°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 13 Dissolve tetrabutyl titanate in isopropanol to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium,
  • the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 75°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 14 Dissolve tetrabutyl titanate in n-butanol to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium,
  • the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 110°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 15 Dissolve tetrabutyl titanate in ethylene glycol to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium,
  • the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 16 Dissolve tetrabutyl titanate to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium.
  • the molar concentration is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 17 Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium hydroxide to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare a solution containing titanium and barium Organosol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol is mixed with potassium sulfate, and the excess organosol is discarded after sedimentation to obtain a mixture of organosol and potassium sulfate, and the excess organosol is discarded.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 18 Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium nitrate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
  • Example 19 Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium carbonate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3.
  • the barium carbonate is reacted with glacial acetic acid to obtain a clear solution, and then an organic solvent is prepared together with tetrabutyl titanate and ethylene glycol methyl ether.
  • the organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate.
  • the mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying.
  • the powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.

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Abstract

Provided is a method for preparing a highly disperse tetragonal-phase barium titanate nanoparticle, comprising: 1) dissolving tetrabutyl titanate in an organic solvent to obtain solution A; adding a barium compound to glacial acetic acid for dissolution or reaction to obtain solution B; and mixing solutions A and B to prepare an organosol containing titanium and barium; 2) mixing the sol with a water-soluble salt, resting or centrifuging same to settle the water-soluble salt, and removing the excess organosol from the upper part to obtain a mixture of the sol and the water-soluble salt; 3) maintaining the temperature, so that sol-gel transition occurs, and drying the gel to coat the surface of the water-soluble salt particle with a dry gel film; 4) performing calcining at a temperature above 600ºC and below the melting point of the salt, so that the dry gel film is converted into a barium titanate nanoparticle to form a calcining product; and 5) performing washing using water and drying to obtain a tetragonal-phase barium titanate nanoparticle. The method enables highly disperse tetragonal-phase barium titanate nanoparticles to be quickly prepared in batches, and the nanoparticles can be used for preparing basic electronic elements such as ultra-thin multilayer ceramic capacitors.

Description

一种制备四方相钛酸钡纳米颗粒的方法Method for preparing tetragonal phase barium titanate nanoparticles 技术领域Technical field
本发明涉及一种制备四方相钛酸钡纳米颗粒的技术，属于电子陶瓷材料制备技术领域。The invention relates to a technology for preparing tetragonal phase barium titanate nanoparticles, and belongs to the technical field of electronic ceramic material preparation.
背景技术Background technique
钛酸钡(BaTiO 3)具有高介电常数和低介电损耗,优良的铁电、压电、耐压和绝缘性能,是电子陶瓷元器件的基础母体原料，被称为电子陶瓷的支柱，广泛地应用于制造高电容电容器、多层基片、各种传感器、半导体材料和敏感元件。随着电子元器件朝着高集成度、高精度和小型化方向的高速发展，需要制备出高分散性和高结晶性的纳米钛酸钡，对纳米钛酸钡制备技术的研究也一直是电子陶瓷材料领域的研究重点。 Barium titanate (BaTiO 3 ) has high dielectric constant and low dielectric loss, excellent ferroelectric, piezoelectric, voltage resistance and insulation properties. It is the basic matrix material of electronic ceramic components and is called the backbone of electronic ceramics. It is widely used in the manufacture of high-capacitance capacitors, multilayer substrates, various sensors, semiconductor materials and sensitive components. With the rapid development of electronic components in the direction of high integration, high precision and miniaturization, it is necessary to prepare nano-barium titanate with high dispersibility and high crystallinity. The research on the preparation technology of nano-barium titanate has always been electronic The research focus in the field of ceramic materials.
目前钛酸钡粉体一般采用高温固相法制备，使用二氧化钛和碳酸钡粉为原料，混合后高温煅烧合成，其合成温度往往高达1400～1500℃，制备出的钛酸钡颗粒粗大，粒径均在微米级。制备纳米钛酸钡颗粒的方法有化学沉淀法、溶胶凝胶(Sol-Gel)法和水热法等，化学沉淀法又包括直接沉淀法、草酸盐共沉淀法、柠檬酸盐法、复合过氧化物法和醇盐水解法等，均是先制备出前驱体，如氢氧化物、草酸盐等，然后在高温下煅烧、反应生成钛酸钡相。溶胶凝胶法是制备出含有钛和钡的凝胶，凝胶经过高温煅烧分解、反应合成得到钛酸钡相。但无论是化学沉淀法还是溶胶凝胶法，均难以避免高温合成过程中纳米颗粒的团聚和烧结，因此难以获得高分散的钛酸钡纳米颗粒。水热法虽然可以制备出分散的钛酸钡纳米颗粒，但由于合成温度太低，难以获得纯四方相的钛酸钡。At present, barium titanate powder is generally prepared by high-temperature solid-phase method, using titanium dioxide and barium carbonate powder as raw materials, and high-temperature calcination synthesis after mixing. The synthesis temperature is often as high as 1400-1500°C. The prepared barium titanate particles are coarse and have a large particle size. All are in the micron level. The methods for preparing nano-barium titanate particles include chemical precipitation, sol-gel (Sol-Gel) and hydrothermal methods. Chemical precipitation also includes direct precipitation, oxalate co-precipitation, citrate, and composite Both the peroxide method and the alkoxide hydrolysis method first prepare precursors, such as hydroxides, oxalates, etc., and then calcinate and react to form barium titanate phase at high temperatures. The sol-gel method is to prepare a gel containing titanium and barium. The gel is calcined and decomposed at a high temperature and synthesized by reaction to obtain a barium titanate phase. However, whether it is a chemical precipitation method or a sol-gel method, it is difficult to avoid the agglomeration and sintering of nanoparticles during the high-temperature synthesis process, so it is difficult to obtain highly dispersed barium titanate nanoparticles. Although the hydrothermal method can prepare dispersed barium titanate nanoparticles, it is difficult to obtain pure tetragonal barium titanate due to the low synthesis temperature.
使用高熔点水溶性盐作为隔离相可以阻止钛酸钡前驱体颗粒的团聚，在高温煅烧过程中能防止钛酸钡颗粒的烧结，且煅烧后容易水洗清除，简便易行。本项目组前期采用微乳液包裹盐壳法(中国专利CN201610365324.4)、含盐水溶胶沉淀法(中国专利CN201610699775.1)、水溶性硫酸盐共沉淀法(中国专利CN201810037875.7)、水溶性盐纳米颗粒隔离法(中国专利CN201810037620.0)和金属乙酰丙酮盐溶液浸渍法(2019101041603)等多种方法，但这些工艺较复杂且难以合成纯相的钛酸钡。The use of a high melting point water-soluble salt as the isolation phase can prevent the barium titanate precursor particles from agglomerating, and can prevent the barium titanate particles from sintering during the high-temperature calcination process, and it is easy to wash and remove after calcination, which is simple and convenient. In the early stage of this project team, microemulsion coating salt shell method (Chinese patent CN201610365324.4), salt-containing sol precipitation method (Chinese patent CN201610699775.1), water-soluble sulfate co-precipitation method (Chinese patent CN201810037875.7), water-soluble salt Nanoparticle isolation method (Chinese patent CN201810037620.0) and metal acetylacetonate solution impregnation method (2019101041603) and other methods, but these processes are more complicated and it is difficult to synthesize pure phase barium titanate.
发明内容Summary of the invention
技术问题：本发明提供了一种能快速合成四方相钛酸钡纳米颗粒的方法，可规模化制备出粒径小于100nm、粒径均匀、分散性好的纯四方钛酸钡纳米颗粒，该制备技术在电子陶瓷领域具有良好的应用前景。Technical problem: The present invention provides a method for rapidly synthesizing tetragonal barium titanate nanoparticles, which can prepare pure tetragonal barium titanate nanoparticles with a particle size of less than 100nm, uniform particle size, and good dispersibility on a large scale. The technology has good application prospects in the field of electronic ceramics.
技术方案：本发明的制备高分散四方相钛酸钡纳米颗粒的方法，包括以下步骤：Technical solution: The method for preparing highly dispersed tetragonal barium titanate nanoparticles of the present invention includes the following steps:
1)将钛酸四丁酯溶于有机溶剂中，得到溶液A；将钡化合物加入到冰乙酸中，溶解或反应后得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，所述有机溶剂为乙二醇甲醚、乙二醇乙醚，乙二醇丁醚，乙醇，正丙醇，异丙醇、正丁醇、乙二醇和丙二醇中的一种；1) Dissolve tetrabutyl titanate in an organic solvent to obtain solution A; add barium compound to glacial acetic acid to dissolve or react to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium , The organic solvent is one of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol and propylene glycol;
2)用含有钛和钡的有机溶胶与水溶性盐混合，静置或离心，使水溶性盐沉降，去除上部多余的有机溶胶，得到含有金属元素的有机溶胶与水溶性盐的混合物；2) Mix the organosol containing titanium and barium with the water-soluble salt, stand or centrifuge to make the water-soluble salt settle, remove the excess organosol from the upper part, and obtain a mixture of the organosol containing metal elements and the water-soluble salt;
3)将该混合物在60℃至120℃保温，发生溶胶-凝胶转变，凝胶干燥后在水溶性盐颗粒表面包覆一层干凝胶膜；3) The mixture is kept at 60°C to 120°C, and a sol-gel transition occurs. After the gel is dried, a layer of dry gel film is coated on the surface of the water-soluble salt particles;
4)将包覆有干凝胶膜的水溶性盐在600℃以上、盐熔点以下煅烧，干凝胶膜转变为钛酸钡纳米颗粒，并分散附着在水溶性盐颗粒表面，形成煅烧产物；4) The water-soluble salt coated with the dry gel film is calcined at a temperature above 600°C and below the melting point of the salt. The dry gel film is converted into barium titanate nanoparticles, which are dispersed and attached to the surface of the water-soluble salt particles to form a calcined product;
5)将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。5) Washing and drying the calcined product with water to obtain tetragonal phase barium titanate nanoparticles.
进一步的，本发明方法中，步骤2)中的水溶性盐为硫酸钾、硫酸钠、氯化钾或氯化钠。Further, in the method of the present invention, the water-soluble salt in step 2) is potassium sulfate, sodium sulfate, potassium chloride or sodium chloride.
进一步的，本发明方法中，步骤1)中的含有钛和钡的有机溶胶中，钛的摩尔浓度在0.01M至1M之间，钛酸四丁酯、乙酸钡和钡化合物的摩尔比为1:1:1-6。Further, in the method of the present invention, in the organosol containing titanium and barium in step 1), the molar concentration of titanium is between 0.01M and 1M, and the molar ratio of tetrabutyl titanate, barium acetate and barium compound is 1. :1:1-6.
进一步的，本发明方法中，步骤1)中的含有钛和钡的有机溶胶中，钡化合物为乙酸钡、氢氧化钡、硝酸钡或碳酸钡。Further, in the method of the present invention, in the organosol containing titanium and barium in step 1), the barium compound is barium acetate, barium hydroxide, barium nitrate or barium carbonate.
有益效果：本发明与现有技术相比，具有以下优点：Beneficial effects: Compared with the prior art, the present invention has the following advantages:
现有的制备钛酸钡纳米颗粒的方法，如化学沉淀法、溶胶凝胶法等，一般是首先制备出前驱体，如金属氢氧化物或金属络合物凝胶等，然后在高温下反应生成钛酸钡颗粒。在高温反应过程中，高表面能的钛酸钡纳米颗粒均会不可避免地会发生团聚和烧结，所以难以制备出高分散的钛酸钡颗粒，而如果降低煅烧温度，又无法得到纯四方相的钛酸钡纳米颗粒。水热法虽然可以得到分散的钛酸钡纳米颗粒，但由于合成温度太低，难以得到纯四方相钛酸钡，而且存在工艺复杂、安全性差的问题。Existing methods for preparing barium titanate nanoparticles, such as chemical precipitation method, sol-gel method, etc., generally first prepare precursors, such as metal hydroxide or metal complex gel, etc., and then react at high temperature Generate barium titanate particles. In the high temperature reaction process, the high surface energy barium titanate nanoparticles will inevitably undergo agglomeration and sintering, so it is difficult to prepare highly dispersed barium titanate particles, and if the calcination temperature is lowered, pure tetragonal phase cannot be obtained. Of barium titanate nanoparticles. Although the hydrothermal method can obtain dispersed barium titanate nanoparticles, because the synthesis temperature is too low, it is difficult to obtain pure tetragonal phase barium titanate, and there are problems of complicated process and poor safety.
使用高熔点水溶性盐作为隔离相可以阻止纳米颗粒在高温下的团聚和烧结，且煅烧后容易水洗清除，工艺简便。本项目组前期尝试过熔盐隔离法、微乳液包裹盐壳法、含盐水溶胶沉淀法、水溶性硫酸盐共沉淀法、水溶性盐纳米颗粒隔离法和金属乙酰丙酮盐溶液浸渍法等多种方法来制备氧化物或复合氧化物纳米颗粒，但这些方法用于制备钛酸钡时遇到了障碍，均难以合成出纯相钛酸钡，得到的纳米颗粒中往往残留二氧化钛等杂相，其原因在于这些方法在高温煅烧时首先生成二氧化钛和氧化钡的混合物，然后二者再发生反应生成钛酸钡，由于颗粒之间接触和反应不充分，极易残留杂相。The use of high melting point water-soluble salt as the isolation phase can prevent the agglomeration and sintering of nanoparticles at high temperatures, and is easy to wash and remove after calcination, and the process is simple and convenient. The project team has tried various methods such as molten salt isolation method, microemulsion coating salt shell method, salt-containing sol precipitation method, water-soluble sulfate co-precipitation method, water-soluble salt nanoparticle isolation method, and metal acetylacetonate solution impregnation method. Methods to prepare oxide or composite oxide nanoparticles, but these methods encountered obstacles when used in the preparation of barium titanate, and it was difficult to synthesize pure phase barium titanate, and the resulting nanoparticles often left miscellaneous phases such as titanium dioxide. The reason The reason is that these methods first generate a mixture of titanium dioxide and barium oxide during high-temperature calcination, and then the two react to form barium titanate. Due to insufficient contact and reaction between particles, it is easy to leave impurity phases.
本发明使用含有钛和钡的有机溶胶来浸渍水溶性盐，有机溶胶在后续的保温过程中发生溶胶-凝胶转变，当凝胶中的有机溶剂蒸发时，凝胶发生收缩，彻底干燥后可在水溶性盐颗粒表面包覆一层干凝胶膜，在后续的高温煅烧过程中，干凝胶膜中的有机物煅烧分解，生成钛酸钡纳米颗粒，而且生成的钛酸钡纳米颗粒分散附着在水溶性盐颗粒的表面，冷却后水洗将盐去除，即可得到具有良好分散性和结晶性的钛酸钡纳米颗粒。在溶胶-凝胶转变过程中，钛离子和钡离子通过络合作用结合在一起，因此可以在600℃以上即可合成纯四方相钛酸钡，彻底解决了杂相残余的问题。The present invention uses organosol containing titanium and barium to impregnate the water-soluble salt. The organosol undergoes a sol-gel transition during the subsequent heat preservation process. When the organic solvent in the gel evaporates, the gel shrinks and can be completely dried. A layer of dry gel film is coated on the surface of the water-soluble salt particles. In the subsequent high-temperature calcination process, the organic matter in the dry gel film is calcined and decomposed to generate barium titanate nanoparticles, and the generated barium titanate nanoparticles are dispersed and attached On the surface of the water-soluble salt particles, the salt is removed by washing with water after cooling, and barium titanate nanoparticles with good dispersibility and crystallinity can be obtained. In the sol-gel transition process, titanium ions and barium ions are combined through complexation, so pure tetragonal phase barium titanate can be synthesized above 600°C, which completely solves the problem of residual phases.
本发明利用了凝胶干燥时的收缩特性，在水溶性盐颗粒表面生成一层均匀的干凝胶膜。高温煅烧时，有机物发生分解，这层干凝胶膜变成钛酸钡纳米颗粒分散在水溶性盐颗粒的表面。我们的研究表明，这些纳米颗粒紧密附着在盐颗粒表面，与水溶性盐颗粒有较强的结合力，不会从盐颗粒表面脱落。同时这些纳米颗粒之间由于相互不接触，因此不会发生扩散传质，也就不会发生团聚和烧结。而且，本发明的煅烧温度高(最高可至硫酸钾熔点)，因此纳米颗粒结晶完善，颗粒内部几乎没有晶体缺陷，也没有残留的立方相钛酸钡。因此，本发明可以得到高分散的纯四方相钛酸钡纳米颗粒。The invention utilizes the shrinkage characteristic of the gel when it is dried to form a uniform dry gel film on the surface of the water-soluble salt particles. During high temperature calcination, organic matter decomposes, and this dry gel film becomes barium titanate nanoparticles dispersed on the surface of the water-soluble salt particles. Our research shows that these nanoparticles are closely attached to the surface of the salt particles, have a strong binding force with the water-soluble salt particles, and will not fall off the surface of the salt particles. At the same time, since these nanoparticles are not in contact with each other, diffusion and mass transfer will not occur, and agglomeration and sintering will not occur. Moreover, the calcination temperature of the present invention is high (up to the melting point of potassium sulfate), so the nano-particles are perfectly crystallized, there are almost no crystal defects inside the particles, and there is no residual cubic barium titanate. Therefore, the present invention can obtain highly dispersed pure tetragonal barium titanate nanoparticles.
经过优选后，本发明使用硫酸钾(熔点1067℃)、硫酸钠(熔点884℃)、氯化钠(熔点801℃)、氯化钾(熔点770℃)这四种水溶性盐来制备钛酸钡纳米颗粒。After optimization, the present invention uses potassium sulfate (melting point 1067°C), sodium sulfate (melting point 884°C), sodium chloride (melting point 801°C), potassium chloride (melting point 770°C) these four water-soluble salts to prepare titanic acid Barium nanoparticles.
如果在有机溶胶中加入表面活性剂，将能进一步改善钛酸钡纳米颗粒的尺寸均匀性。表面活性剂包括聚乙二醇、聚乙烯吡咯烷酮、羧酸类表面活性剂等。If a surfactant is added to the organosol, the size uniformity of the barium titanate nanoparticles will be further improved. Surfactants include polyethylene glycol, polyvinylpyrrolidone, carboxylic acid surfactants and the like.
本发明可以快速批量制备出分散性良好的纯四方相钛酸钡纳米颗粒，解决纳米颗粒的团聚和烧结问题。The invention can quickly prepare pure tetragonal barium titanate nanoparticles with good dispersibility in batches, and solve the problems of agglomeration and sintering of the nanoparticles.
在本发明所述的有机溶胶中溶入含有La、Ce、Al、Mn、Nd等元素的金属盐，可以实现对钛酸钡的掺杂。The metal salt containing La, Ce, Al, Mn, Nd and other elements is dissolved in the organosol of the present invention to realize the doping of barium titanate.
本发明制备方法简便，易于大规模生产。The preparation method of the invention is simple and easy to produce on a large scale.
附图说明Description of the drawings
图1使用本发明方法在900℃制备的钛酸钡纳米颗粒，粒径约60-80nm，分散性良好。Fig. 1 Barium titanate nanoparticles prepared at 900° C. using the method of the present invention have a particle size of about 60-80 nm and good dispersibility.
图2为钛酸钡纳米颗粒在盐颗粒表面的分布状态，钛酸钡纳米颗粒呈分散分布。Figure 2 shows the distribution of barium titanate nanoparticles on the surface of salt particles, and the barium titanate nanoparticles are dispersed.
具体实施方式Detailed ways
下面结合实施例和说明书附图对本发明作进一步的说明。The present invention will be further explained below in conjunction with the embodiments and the drawings of the specification.
实施例1：将钛酸四丁酯溶于乙二醇甲醚中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 1: Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例2：将钛酸四丁酯溶于乙二醇甲醚中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸纳混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钠熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 2: Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and sodium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of sodium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例3：将钛酸四丁酯溶于乙二醇甲醚中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和氯化钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至氯化钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 3: Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium chloride are mixed, and the excess organosol is discarded after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium chloride, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例4：将钛酸四丁酯溶于乙二醇甲醚中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和氯化钠混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至氯化钠熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 4: Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol is mixed with sodium chloride, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of sodium chloride, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例5：将钛酸四丁酯溶于乙二醇甲醚中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.01M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 5: Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.01M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例6：将钛酸四丁酯溶于乙二醇甲醚中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 6: Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例7：将钛酸四丁酯溶于乙二醇甲醚中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:1。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 7: Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:1. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例8：将钛酸四丁酯溶于乙二醇甲醚中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:6。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 8: Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, in which the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:6. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例9：将钛酸四丁酯溶于乙二醇乙醚中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 9: Dissolve tetrabutyl titanate in ethylene glycol ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium , Wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例10：将钛酸四丁酯溶于乙二醇丁醚中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 10: Dissolve tetrabutyl titanate in ethylene glycol butyl ether to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例11：将钛酸四丁酯溶于乙醇中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至75℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 11: Dissolve tetrabutyl titanate in ethanol to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium, in which titanium The molar concentration of is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 75°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例12：将钛酸四丁酯溶于正丙醇中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至90℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 12: Dissolve tetrabutyl titanate in n-propanol to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium, The molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 90°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例13：将钛酸四丁酯溶于异丙醇中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至75℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 13: Dissolve tetrabutyl titanate in isopropanol to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium, The molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 75°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例14：将钛酸四丁酯溶于正丁醇中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至110℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 14: Dissolve tetrabutyl titanate in n-butanol to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium, The molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 110°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例15：将钛酸四丁酯溶于乙二醇中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 15: Dissolve tetrabutyl titanate in ethylene glycol to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium, The molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例16：将钛酸四丁酯溶于中，得到溶液A；将乙酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 16: Dissolve tetrabutyl titanate to obtain solution A; add barium acetate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium. The molar concentration is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例17：将钛酸四丁酯溶于乙二醇甲醚中，得到溶液A；将氢氧化钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物，倒掉多余的有机溶胶。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 17: Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium hydroxide to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare a solution containing titanium and barium Organosol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol is mixed with potassium sulfate, and the excess organosol is discarded after sedimentation to obtain a mixture of organosol and potassium sulfate, and the excess organosol is discarded. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例18：将钛酸四丁酯溶于乙二醇甲醚中，得到溶液A；将硝酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 18: Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium nitrate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.
实施例19：将钛酸四丁酯溶于乙二醇甲醚中，得到溶液A；将碳酸钡加入到冰乙酸中，得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，其中钛的摩尔浓度为0.1M，钛酸四丁酯、乙酸钡和冰乙酸的摩尔比为1:1:3。先将碳酸钡与冰乙酸反应得到澄清溶液，再与钛酸四丁酯和乙二醇甲醚一起配制出有机溶剂。用该有机溶胶和硫酸钾混合，沉降后倒掉多余的有机溶胶，得到有机溶胶和硫酸钾的混合物。将该混合物在60℃至120℃保温，干燥后得到松散粉末。将粉末在600℃至硫酸钾熔点以下煅烧，将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。Example 19: Dissolve tetrabutyl titanate in ethylene glycol methyl ether to obtain solution A; add barium carbonate to glacial acetic acid to obtain solution B; mix solution A and solution B to prepare an organic compound containing titanium and barium Sol, wherein the molar concentration of titanium is 0.1M, and the molar ratio of tetrabutyl titanate, barium acetate and glacial acetic acid is 1:1:3. First, the barium carbonate is reacted with glacial acetic acid to obtain a clear solution, and then an organic solvent is prepared together with tetrabutyl titanate and ethylene glycol methyl ether. The organosol and potassium sulfate are mixed, and the excess organosol is poured out after sedimentation to obtain a mixture of organosol and potassium sulfate. The mixture is kept at 60°C to 120°C, and a loose powder is obtained after drying. The powder is calcined at 600° C. to below the melting point of potassium sulfate, and the calcined product is washed with water and dried to obtain tetragonal barium titanate nanoparticles.

Claims (4)

  1. 一种制备高分散四方相钛酸钡纳米颗粒的方法，其特征在于，该方法包括以下步骤：A method for preparing highly dispersed tetragonal barium titanate nanoparticles, which is characterized in that the method includes the following steps:
    1)将钛酸四丁酯溶于有机溶剂中，得到溶液A；将钡化合物加入到冰乙酸中，溶解或反应后得到溶液B；将溶液A和溶液B混合配制含有钛和钡的有机溶胶，所述有机溶剂为乙二醇甲醚、乙二醇乙醚，乙二醇丁醚，乙醇，正丙醇，异丙醇、正丁醇、乙二醇和丙二醇中的一种；1) Dissolve tetrabutyl titanate in an organic solvent to obtain solution A; add barium compound to glacial acetic acid to dissolve or react to obtain solution B; mix solution A and solution B to prepare an organosol containing titanium and barium , The organic solvent is one of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol and propylene glycol;
    2)用含有钛和钡的有机溶胶与水溶性盐混合，静置或离心，使水溶性盐沉降，去除上部多余的有机溶胶，得到含有钛和钡的有机溶胶与水溶性盐的混合物；2) Mix the organosol containing titanium and barium with the water-soluble salt, stand still or centrifuge to make the water-soluble salt settle, remove the excess organosol from the upper part, and obtain a mixture of the organosol containing titanium and barium and the water-soluble salt;
    3)将该混合物在60℃至120℃保温，发生溶胶-凝胶转变，凝胶干燥后在水溶性盐颗粒表面包覆一层干凝胶膜；3) The mixture is kept at 60°C to 120°C, and a sol-gel transition occurs. After the gel is dried, a layer of dry gel film is coated on the surface of the water-soluble salt particles;
    4)将包覆有干凝胶膜的水溶性盐在600℃以上、盐熔点以下煅烧，干凝胶膜转变为钛酸钡纳米颗粒，并分散附着在水溶性盐颗粒表面，形成煅烧产物；4) The water-soluble salt coated with the dry gel film is calcined at a temperature above 600°C and below the melting point of the salt. The dry gel film is converted into barium titanate nanoparticles, which are dispersed and attached to the surface of the water-soluble salt particles to form a calcined product;
    5)将煅烧产物用水洗涤、干燥，得到四方相钛酸钡纳米颗粒。5) Washing and drying the calcined product with water to obtain tetragonal phase barium titanate nanoparticles.
  2. 根据权利要求1所述的一种制备高分散四方相钛酸钡纳米颗粒的方法，其特征在于，所述水溶性盐为硫酸钾、硫酸钠、氯化钾或氯化钠。The method for preparing highly dispersed tetragonal barium titanate nanoparticles according to claim 1, wherein the water-soluble salt is potassium sulfate, sodium sulfate, potassium chloride or sodium chloride.
  3. 根据权利要求1所述的一种制备高分散四方相钛酸钡纳米颗粒的方法，其特征在于，所述含有钛和钡的有机溶胶中，钛的摩尔浓度在0.01M至1M之间，钛酸四丁酯、钡化合物和冰乙酸的摩尔比为1:1:1-6。The method for preparing highly dispersed tetragonal barium titanate nanoparticles according to claim 1, wherein in the organosol containing titanium and barium, the molar concentration of titanium is between 0.01M and 1M. The molar ratio of tetrabutyl acid, barium compound and glacial acetic acid is 1:1:1-6.
  4. 根据权利要求1所述的一种制备高分散四方相钛酸钡纳米颗粒的方法，其特征在于，所述钡化合物为乙酸钡、氢氧化钡、硝酸钡或碳酸钡。The method for preparing highly dispersed tetragonal barium titanate nanoparticles according to claim 1, wherein the barium compound is barium acetate, barium hydroxide, barium nitrate or barium carbonate.
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