CN102432283B - Preparation method of grain boundary layer type structure BaTiO3 composite membrane - Google Patents
Preparation method of grain boundary layer type structure BaTiO3 composite membrane Download PDFInfo
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- CN102432283B CN102432283B CN 201110242762 CN201110242762A CN102432283B CN 102432283 B CN102432283 B CN 102432283B CN 201110242762 CN201110242762 CN 201110242762 CN 201110242762 A CN201110242762 A CN 201110242762A CN 102432283 B CN102432283 B CN 102432283B
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Abstract
The invention discloses a preparation method of a grain boundary layer type structure BaTiO3 composite membrane. In the prepared grain boundary layer type structure, a core is made of barium titanate, a shell layer is made of copper oxide, polystyrene is firstly adopted to wrap the barium titanate to prepare core shell structure microspheres which are utilized to prepare colloid crystals, non-close packed opal type colloid crystals are obtained after the shell layer polystyrene is calcinated to be removed, the non-close packed opal type colloid crystals are soaked in a prepared copper oxide reaction precursor, and the grain boundary layer type structure BaTiO3 composite membrane is obtained after glue drying and calcination.
Description
Technical field
The present invention relates to a kind of preparation method of ceramic membrane, particularly a kind of crystal boundary layer structure BaTiO
3The preparation method of composite membrane.
Background technology
Along with the development of electronics technology to miniaturization, densification, electronic ceramics receives publicity with performances such as the electricity of its uniqueness, magnetic, sound, light, heat, power.According to structure and principle, semiconductor ceramic capacitor can be divided into surperficial stratotype and crystal boundary stratotype two classes, the surface stratotype is to form insulation layer as medium layer on the surface of semiconductor ceramic material, boundary layer type then is the grain boundaries formation insulation layer at the semiconductor transformation ceramic crystal, thereby forms the capacitor network of a plurality of series and parallels.The series-parallel connection of device finally obtains very high specific inductivity.BaTiO
3Be a kind of ferroelectric material with very high dielectric constant, in laminated ceramic capacitor and dielectric amplifier, be widely used.But BaTiO
3Sintering temperature higher, therefore the sintering process of early stage boundary layer ceramic capacitor all is that high temperature secondary is burnt till, this not only can increase energy consumption, causes environmental pollution, and uses high temperature silver slurry and have higher cost.And adopt doping vario-property, adding fusing assistant, formation low temperature glass to equate to reduce BaTiO
3The method of sintering temperature owing to be subject to the impact of powder purity, the unequal factor of globule size, is difficult between the particle mix, and causes microstructural inequality.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of crystal boundary layer structure BaTiO
3The preparation method of composite membrane prepares the product grain size, is evenly distributed, and in conjunction with tight, and production technique is simple, the cycle is short, required equipment is simple, and energy consumption is low.
To achieve these goals, the technical solution used in the present invention is:
Crystal boundary layer structure BaTiO
3The preparation method of composite membrane may further comprise the steps:
The first step, it is in 25～28% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1: 1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1: 1.5～2.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/3～1/2, and transfer pH value to 5.0～7.0 with ammoniacal liquor, the polyoxyethylene glycol that adds again citric acid total mass 1/3～1/2, stir, be evaporated to wet gel through 80～90 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 700～750 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 3～5g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=2～3: 1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1～2mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 1～2% of vinylbenzene mixeding liquid volume, behind reaction 20～24h, throw out is used respectively toluene and absolute ethanol washing, at 35～40 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel, wherein: n
VinylbenzeneRepresent cinnamic amount of substance, n
Barium titanateThe amount of substance of expression barium titanate;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in organic solvent, ultrasonic time is 2～3h, obtain suspension, the massfraction of its particle is 1%～2%, substrate is dipped vertically into places stably in the suspension, 40～50 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal at substrate surface;
In the 4th step, the nucleocapsid structure colloidal crystal at 400～500 ℃ of lower calcining 4～6h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1: 2, lifts membrane behind the reaction 30min, 100～150 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1150～1250 ℃ of calcinings again
3Composite membrane.
Organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol in described the 3rd step.
Substrate is slide glass, ito glass or silicon chip in described the 3rd step.
After lifting membrane in described the 5th step, draw first the colloid of surface excess with filter paper, then just carry out drying.
Compared with prior art, the present invention forms core-shell structure particles with polystyrene parcel barium titanate particles, the core-shell structure particles assembling is formed colloidal crystal, after removing polystyrene, calcining obtains again non-close heap opal type barium titanate colloidal crystal, again it is immersed in the cupric nitrate saturated solution, after precipitin reaction, drying and dehydrating, calcining, namely obtain again crystal boundary layer structure BaTiO
3Composite membrane.Like this each grain size in the grain boundary layer type structure ceramic membrane, be evenly distributed, in conjunction with closely, and avoided being difficult to form such as barium titanate one class crystal boundary and the inner oxygen velocity of diffusion of crystal grain material too fast and that two speed differ too little the situation of nucleocapsid structure.
Embodiment
Below in conjunction with embodiment the present invention is described in further details.
Embodiment one
Crystal boundary layer structure BaTiO
3The preparation method of composite membrane may further comprise the steps:
The first step, it is in 28% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1: 1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1: 1.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/3, and transfer pH value to 7.0 with ammoniacal liquor, the polyoxyethylene glycol that adds again citric acid total mass 1/2, stir, be evaporated to wet gel through 80 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 750 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 5g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=3: 1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 2% of vinylbenzene mixeding liquid volume, behind the reaction 20h, throw out is used respectively toluene and absolute ethanol washing, at 35 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in ethanol, ultrasonic time is 2h, obtain suspension, the massfraction of its particle is 2%, slide glass is dipped vertically into places stably in the suspension, 40 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal in slide surface;
In the 4th step, the nucleocapsid structure colloidal crystal at 400 ℃ of lower calcining 6h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1: 2, lifts membrane behind the reaction 30min, 100 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1150 ℃ of calcinings again
3Composite membrane.
Embodiment two
Crystal boundary layer structure BaTiO
3The preparation method of composite membrane may further comprise the steps:
The first step, it is in 28% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1: 1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1: 2.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/2, and transfer pH value to 5.0 with ammoniacal liquor, the polyoxyethylene glycol that adds again citric acid total mass 1/2, stir, be evaporated to wet gel through 80 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 700 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 5g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=3: 1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 2mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 2% of vinylbenzene mixeding liquid volume, behind the reaction 24h, throw out is used respectively toluene and absolute ethanol washing, at 40 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in methyl alcohol, ultrasonic time is 3h, obtain suspension, the massfraction of its particle is 1%, ito glass is dipped vertically into places stably in the suspension, 50 ℃ of lower vacuum-dryings, after solution evaporates fully, go out one deck nucleocapsid structure colloidal crystal in the ito glass surface growth;
In the 4th step, the nucleocapsid structure colloidal crystal at 500 ℃ of lower calcining 4h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1: 2, lifts membrane behind the reaction 30min, 150 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1250 ℃ of calcinings again
3Composite membrane.
Embodiment three
Crystal boundary layer structure BaTiO
3The preparation method of composite membrane may further comprise the steps:
The first step, it is in 25% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1: 1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1: 2.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/2, and transfer pH value to 6.0 with ammoniacal liquor, the polyoxyethylene glycol that adds again citric acid total mass 1/3, stir, be evaporated to wet gel through 90 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 700 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 3g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=2: 1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 1% of vinylbenzene mixeding liquid volume, behind the reaction 24h, throw out is used respectively toluene and absolute ethanol washing, at 35 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in acetone, ultrasonic time is 2h, obtain suspension, the massfraction of its particle is 2%, silicon chip is dipped vertically into places stably in the suspension, 50 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal at silicon chip surface;
In the 4th step, the nucleocapsid structure colloidal crystal at 450 ℃ of lower calcining 5h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1: 2, lifts membrane behind the reaction 30min, 100 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1250 ℃ of calcinings again
3Composite membrane.
Embodiment four
Crystal boundary layer structure BaTiO
3The preparation method of composite membrane may further comprise the steps:
The first step, it is in 26% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1: 1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1: 1.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/2, and transfer pH value to 5.0 with ammoniacal liquor, the polyoxyethylene glycol that adds again citric acid total mass 1/2, stir, be evaporated to wet gel through 85 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 720 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 5g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=3: 1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1.5mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 1% of vinylbenzene mixeding liquid volume, behind the reaction 20h, throw out is used respectively toluene and absolute ethanol washing, at 35 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in acetonitrile, ultrasonic time is 3h, obtain suspension, the massfraction of its particle is 2%, slide glass is dipped vertically into places stably in the suspension, 45 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal in slide surface;
In the 4th step, the nucleocapsid structure colloidal crystal at 450 ℃ of lower calcining 4h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1: 2, lifts membrane behind the reaction 30min, 120 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1200 ℃ of calcinings again
3Composite membrane.
Embodiment five
Crystal boundary layer structure BaTiO
3The preparation method of composite membrane may further comprise the steps:
The first step, it is in 27% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1: 1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1: 2, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/2, and transfer pH value to 6.0 with ammoniacal liquor, the polyoxyethylene glycol that adds again citric acid total mass 1/2, stir, be evaporated to wet gel through 80 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 700 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 4g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=2.5: 1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 2% of vinylbenzene mixeding liquid volume, behind the reaction 20h, throw out is used respectively toluene and absolute ethanol washing, at 35 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in Virahol, ultrasonic time is 3h, obtain suspension, the massfraction of its particle is 1%, ito glass is dipped vertically into places stably in the suspension, 40 ℃ of lower vacuum-dryings, after solution evaporates fully, go out one deck nucleocapsid structure colloidal crystal in the ito glass surface growth;
In the 4th step, the nucleocapsid structure colloidal crystal at 500 ℃ of lower calcining 6h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1: 2, lifts membrane behind the reaction 30min, 150 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1150 ℃ of calcinings again
3Composite membrane.
Embodiment six
Crystal boundary layer structure BaTiO
3The preparation method of composite membrane may further comprise the steps:
The first step, it is in 28% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1: 1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1: 2.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/2, and transfer pH value to 5.0 with ammoniacal liquor, the polyoxyethylene glycol that adds again citric acid total mass 1/3, stir, be evaporated to wet gel through 80 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 750 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 5g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=2: 1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 1% of vinylbenzene mixeding liquid volume, behind the reaction 24h, throw out is used respectively toluene and absolute ethanol washing, at 35 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in ethanol, ultrasonic time is 2h, obtain suspension, the massfraction of its particle is 1%, silicon chip is dipped vertically into places stably in the suspension, 50 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal at silicon chip surface;
In the 4th step, the nucleocapsid structure colloidal crystal at 400 ℃ of lower calcining 6h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1: 2, lifts membrane behind the reaction 30min, 100 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1250 ℃ of calcinings again
3Composite membrane.
More than among each embodiment, the organic solvent that the spherical particles ultra-sonic dispersion is used can also have other multiple choices; Among each embodiment, substrate can be slide glass, ito glass or silicon chip etc.
Claims (9)
1. crystal boundary layer structure BaTiO
3The preparation method of composite membrane is characterized in that, may further comprise the steps:
The first step, it is in 25～28% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1:1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1:1.5～2.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/3～1/2, and with ammoniacal liquor adjust pH to 5.0～7.0, the polyoxyethylene glycol that adds again citric acid total mass 1/3～1/2, stir, be evaporated to wet gel through 80～90 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 700～750 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 3～5g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=2～3:1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1～2mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 1～2% of vinylbenzene mixeding liquid volume, behind reaction 20～24h, throw out is used respectively toluene and absolute ethanol washing, at 35～40 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel, wherein: n
VinylbenzeneRepresent cinnamic amount of substance, n
Barium titanateThe amount of substance of expression barium titanate;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in organic solvent, ultrasonic time is 2～3h, obtain suspension, the massfraction of its particle is 1%～2%, substrate is dipped vertically into places stably in the suspension, 40～50 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal at substrate surface;
In the 4th step, the nucleocapsid structure colloidal crystal at 400～500 ℃ of lower calcining 4～6h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1:2, lifts membrane behind the reaction 30min, 100～150 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1150～1250 ℃ of calcinings again
3Composite membrane;
Organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol in described the 3rd step.
2. crystal boundary layer structure BaTiO according to claim 1
3The preparation method of composite membrane is characterized in that, substrate is slide glass, ito glass or silicon chip in described the 3rd step.
3. crystal boundary layer structure BaTiO according to claim 1
3The preparation method of composite membrane is characterized in that, lift membrane in described the 5th step after, draw first the colloid of surface excess with filter paper, then just carry out drying.
4. crystal boundary layer structure BaTiO
3The preparation method of composite membrane is characterized in that, may further comprise the steps:
The first step, it is in 28% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1:1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1:1.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/3, and with ammoniacal liquor adjust pH to 7.0, the polyoxyethylene glycol that adds again citric acid total mass 1/2, stir, be evaporated to wet gel through 80 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 750 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 5g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=3:1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 2% of vinylbenzene mixeding liquid volume, behind the reaction 20h, throw out is used respectively toluene and absolute ethanol washing, at 35 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel, wherein: n
VinylbenzeneRepresent cinnamic amount of substance, n
Barium titanateThe amount of substance of expression barium titanate;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in organic solvent, ultrasonic time is 2h, obtains suspension, and the massfraction of its particle is 2%, substrate is dipped vertically into places stably in the suspension, 40 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal at substrate surface, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol, and substrate is slide glass, ito glass or silicon chip;
In the 4th step, the nucleocapsid structure colloidal crystal at 400 ℃ of lower calcining 6h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1:2, lifts membrane behind the reaction 30min, 100 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1150 ℃ of calcinings again
3Composite membrane.
5. crystal boundary layer structure BaTiO
3The preparation method of composite membrane is characterized in that, may further comprise the steps:
The first step, it is in 28% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1:1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1:2.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/2, and with ammoniacal liquor adjust pH to 5.0, the polyoxyethylene glycol that adds again citric acid total mass 1/2, stir, be evaporated to wet gel through 80 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 700 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 5g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=3:1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 2mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 2% of vinylbenzene mixeding liquid volume, behind the reaction 24h, throw out is used respectively toluene and absolute ethanol washing, at 40 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel, wherein: n
VinylbenzeneRepresent cinnamic amount of substance, n
Barium titanateThe amount of substance of expression barium titanate;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in organic solvent, ultrasonic time is 3h, obtains suspension, and the massfraction of its particle is 1%, substrate is dipped vertically into places stably in the suspension, 50 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal at substrate surface, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol, and substrate is slide glass, ito glass or silicon chip;
In the 4th step, the nucleocapsid structure colloidal crystal at 500 ℃ of lower calcining 4h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1:2, lifts membrane behind the reaction 30min, 150 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1250 ℃ of calcinings again
3Composite membrane.
6. crystal boundary layer structure BaTiO
3The preparation method of composite membrane is characterized in that, may further comprise the steps:
The first step, it is in 25% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1:1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1:2.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/2, and with ammoniacal liquor adjust pH to 6.0, the polyoxyethylene glycol that adds again citric acid total mass 1/3, stir, be evaporated to wet gel through 90 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 700 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 3g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=2:1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 1% of vinylbenzene mixeding liquid volume, behind the reaction 24h, throw out is used respectively toluene and absolute ethanol washing, at 35 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel, wherein: n
VinylbenzeneRepresent cinnamic amount of substance, n
Barium titanateThe amount of substance of expression barium titanate;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in organic solvent, ultrasonic time is 2h, obtains suspension, and the massfraction of its particle is 2%, substrate is dipped vertically into places stably in the suspension, 50 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal at substrate surface, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol, and substrate is slide glass, ito glass or silicon chip;
In the 4th step, the nucleocapsid structure colloidal crystal at 450 ℃ of lower calcining 5h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1:2, lifts membrane behind the reaction 30min, 100 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1250 ℃ of calcinings again
3Composite membrane.
7. crystal boundary layer structure BaTiO
3The preparation method of composite membrane is characterized in that, may further comprise the steps:
The first step, it is in 26% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1:1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1:1.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/2, and with ammoniacal liquor adjust pH to 5.0, the polyoxyethylene glycol that adds again citric acid total mass 1/2, stir, be evaporated to wet gel through 85 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 720 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 5g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=3:1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1.5mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 1% of vinylbenzene mixeding liquid volume, behind the reaction 20h, throw out is used respectively toluene and absolute ethanol washing, at 35 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel, wherein: n
VinylbenzeneRepresent cinnamic amount of substance, n
Barium titanateThe amount of substance of expression barium titanate;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in organic solvent, ultrasonic time is 3h, obtains suspension, and the massfraction of its particle is 2%, substrate is dipped vertically into places stably in the suspension, 45 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal at substrate surface, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol, and substrate is slide glass, ito glass or silicon chip;
In the 4th step, the nucleocapsid structure colloidal crystal at 450 ℃ of lower calcining 4h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1:2, lifts membrane behind the reaction 30min, 120 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1200 ℃ of calcinings again
3Composite membrane.
8. crystal boundary layer structure BaTiO
3The preparation method of composite membrane is characterized in that, may further comprise the steps:
The first step, it is in 27% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1:1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1:2, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/2, and with ammoniacal liquor adjust pH to 6.0, the polyoxyethylene glycol that adds again citric acid total mass 1/2, stir, be evaporated to wet gel through 80 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 700 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 4g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=2.5:1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 2% of vinylbenzene mixeding liquid volume, behind the reaction 20h, throw out is used respectively toluene and absolute ethanol washing, at 35 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel, wherein: n
VinylbenzeneRepresent cinnamic amount of substance, n
Barium titanateThe amount of substance of expression barium titanate;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in organic solvent, ultrasonic time is 3h, obtains suspension, and the massfraction of its particle is 1%, substrate is dipped vertically into places stably in the suspension, 40 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal at substrate surface, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol, and substrate is slide glass, ito glass or silicon chip;
In the 4th step, the nucleocapsid structure colloidal crystal at 500 ℃ of lower calcining 6h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1:2, lifts membrane behind the reaction 30min, 150 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1150 ℃ of calcinings again
3Composite membrane.
9. crystal boundary layer structure BaTiO
3The preparation method of composite membrane is characterized in that, may further comprise the steps:
The first step, it is in 28% the ammoniacal liquor that two parts of citric acids of equivalent are dissolved in respectively mass concentration, ammoniacal liquor is as the criterion can dissolve citric acid, the butyl (tetra) titanate and the barium acetate that with mol ratio are again 1:1 are dissolved in respectively formation solution A and solution B in above-mentioned two parts of citric acid solutions, the mole number sum of butyl (tetra) titanate and barium acetate and the mol ratio of citric acid total amount are 1:2.5, solution A is fully mixed with solution B, the dehydrated alcohol that adds ammoniacal liquor volume total amount 1/2, and with ammoniacal liquor adjust pH to 5.0, the polyoxyethylene glycol that adds again citric acid total mass 1/3, stir, be evaporated to wet gel through 80 ℃ of water-baths, will obtain barium titanate particles after 150 ℃ of dryings of wet gel and 750 ℃ of calcinings again;
Second step, the barium titanate particles ultra-sonic dispersion that 5g is made adds vinylbenzene under the continuously stirring in the 50ml Virahol, and wherein mol ratio is n
Vinylbenzene: n
Barium titanate=2:1, logical nitrogen, dripping concentration in 65 ℃ of lower backflow situations is benzoyl peroxide-aqueous isopropanol of 1mol/L, wherein benzoyl peroxide-aqueous isopropanol volume is 1% of vinylbenzene mixeding liquid volume, behind the reaction 24h, throw out is used respectively toluene and absolute ethanol washing, at 35 ℃ of lower dry barium titanate particles that namely obtain the polystyrene parcel, wherein: n
VinylbenzeneRepresent cinnamic amount of substance, n
Barium titanateThe amount of substance of expression barium titanate;
The 3rd step, with the barium titanate particles ultra-sonic dispersion of prepared polystyrene parcel in organic solvent, ultrasonic time is 2h, obtains suspension, and the massfraction of its particle is 1%, substrate is dipped vertically into places stably in the suspension, 50 ℃ of lower vacuum-dryings, after solution evaporates fully, grow one deck nucleocapsid structure colloidal crystal at substrate surface, described organic solvent is ethanol, methyl alcohol, acetone, acetonitrile or Virahol, and substrate is slide glass, ito glass or silicon chip;
In the 4th step, the nucleocapsid structure colloidal crystal at 400 ℃ of lower calcining 6h, is namely obtained non-close heap opal BaTiO
3Colloidal crystal;
The 5th step is with non-close heap opal BaTiO
3Colloidal crystal immerses the saturated solution of cupric nitrate, being added dropwise to concentration under ultrasonic agitation is 2mol/LNaOH solution, and the mol ratio of cupric nitrate and NaOH is 1:2, lifts membrane behind the reaction 30min, 100 ℃ of lower drying and dehydratings namely get crystal boundary layer structure BaTiO through 1250 ℃ of calcinings again
3Composite membrane.
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| CN103880066B (en) * | 2014-02-19 | 2015-05-20 | 陕西科技大学 | Preparation method of cubic phase BaTiO3 hollow nanospheres |
| CN103880015B (en) * | 2014-02-19 | 2015-11-18 | 陕西科技大学 | The preparation method of the heterogeneous colloidal crystal of a kind of silicon oxide-barium titanate |
| CN103880018B (en) * | 2014-02-19 | 2015-09-30 | 陕西科技大学 | A kind of SiO 2-SiO 2the preparation method of the two sized colloidal crystal of homogeneity |
| CN103880014B (en) * | 2014-02-19 | 2015-09-30 | 陕西科技大学 | A kind of SiO 2-BaTiO 3the preparation method of two sized colloidal crystal |
| CN103831436B (en) * | 2014-03-21 | 2015-09-30 | 哈尔滨工业大学 | The preparation method of nucleocapsid structure Cu/BaTiO3 composite granule |
| CN105665699A (en) * | 2016-03-16 | 2016-06-15 | 哈尔滨理工大学 | Preparation method of nanocopper coated BaTiO3 conductive microsphere and application thereof |
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