CN101423249B - Monodisperse pure rutile type or rutile type and anatase type composite phase titanium dioxide hollow submicron sphere and preparation method thereof - Google Patents
Monodisperse pure rutile type or rutile type and anatase type composite phase titanium dioxide hollow submicron sphere and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000004793 Polystyrene Substances 0.000 claims abstract description 51
- 229920002223 polystyrene Polymers 0.000 claims abstract description 47
- 239000002105 nanoparticle Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 25
- 239000004575 stone Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 description 54
- 229910010413 TiO 2 Inorganic materials 0.000 description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 22
- 238000000280 densification Methods 0.000 description 18
- 239000004005 microsphere Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000012463 white pigment Substances 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- -1 transmitter Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention belongs to the field of nano materials, and relates to monodisperse pure rutile type or rutile type and anatase type composite phase titanium dioxide hollow submicron spheres; and monodisperse submicron spheres with core/shell structures formed by coating polystyrene spheres with anatase titanium dioxide nanoparticles. Mixing PS/TiO2The submicron spheres are subjected to hydrothermal treatment to obtain submicron spheres with a core/shell structure formed by polystyrene spheres coated with anatase type titanium dioxide nanoparticles, and then high-temperature sintering is carried out to obtain monodisperse pure rutile type or rutile type and anatase type composite phase titanium dioxide hollow submicron spheres with rough surfaces. By direct high temperature sintering of PS/TiO2The submicron spheres synthesize monodisperse pure rutile type or rutile type and anatase type composite phase titanium dioxide hollow submicron spheres with smooth and compact surfaces. The titanium dioxide hollow submicron sphere can be widely applied to the fields of coatings, sensors, chemical fibers, printing ink, functional ceramics, electronic paper, drug slow release and the like.
Description
Technical field
The invention belongs to technical field of nano material, particularly relate to red stone type of monodisperse pure or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball; And the anatase titanium dioxide nano particle coats the sub-micron ball of the formed single dispersion of polystyrene spheres, core/shell structure.
Background technology
Titanium dioxide is commonly called as titanium white, is that titanium is one of most important product, and Detitanium-ore-type (Anatase is designated hereinafter simply as the A type), brookite type (Brookite is designated hereinafter simply as Type B) and three kinds of crystal formations of rutile-type (Rutile is designated hereinafter simply as the R type) are arranged.Type B titanium dioxide belongs to rhombic system, and the titanium dioxide of A and R structure belongs to tetragonal system.As a rule, R type titanium dioxide is thermodynamically stable phase, and the A type is a metastable phase, and the phase transformation from A to R is the irreversible transition of metastable phase to stable phase.Initial transformation temperature is different because of preparation condition and globule size, usually between 800～1200 ℃.Nano level TiO
2Invert point relatively low, usually at 500～1000 ℃.Anatase titanium dioxide (A-TiO
2) and rutile titanium dioxide (R-TiO
2) because its structure difference causes both to exist evident difference on physics and chemical property.A-TiO
2Luminance factor R-TiO in visible light shortwave part
2High and lower than R type to ultraviolet receptivity, so photocatalytic activity is than the height of R type.But the R type is more stable and fine and close than A type, and higher density, hardness, specific inductivity and specific refractory power are arranged, and its opacifying power and tinting strength are also than A type TiO
2High.So A type TiO
2Often be used in photocatalysis field, and R type TiO
2Because chemical stability is higher relatively, in fields such as coating, pigment, printing ink, fine ceramics, technique of display purposes is widely arranged.Generally speaking, owing to having particular performances such as good weather resisteant, erosion resistance, higher chemical stability, thermostability, nontoxic, high dispersive, titanium dioxide is widely used in fields such as coating, transmitter, chemical fibre, printing ink, function ceramics.Especially because titanium dioxide dielectric coefficient height, specific refractory power height, color and luster is pure white, chemical stability good, be a kind of ideal white display material, in the Electronic Paper field, be widely used as white electrophoretic particles in recent years.But because its density is bigger, long-time placement precipitates from electrophoresis disclosing solution easily separates out, and this has reduced the display quality of Electronic Paper to a great extent.In order to reduce TiO
2Density, often adopt following two kinds of methods: the low density superpolymer coats method and sacrifices template (sacrifice template and obtain hollow ball).Though first method can effectively reduce the density of titanium dioxide, because the specific refractory power of coating is lower usually, this has reduced the specific refractory power of titanium dioxide to a certain extent.As for second method, at first to synthesize core/shell structure, the template of removing as nuclear by high-temperature sintering process or dissolution with solvents method obtains the hollow titanium dioxide ball then, thereby reduces the density of titanium dioxide.Yet, the normally A-TiO that obtains by second method
2Hollow ball does not still have pure R-TiO up to now
2The report of hollow ball document.Tracing it to its cause is temperature when higher, often causes hollow ball to be caved in, and has lost hollow structure, and temperature is too low then can not to be converted into the rutile phase.On the other hand, because A-TiO
2Be a kind of photocatalyst material of excellence, often cause the organic dye molecule photochemical catalysis variable color in the electrophoresis liquid, and then influence the display quality of Electronic Paper.Present, develop the white pigment that a kind of density is low, chemical stability is high and remain challenge very big in the technique of display field.
Because hollow titanium dioxide is very active to its research both at home and abroad in the important application of various fields.As general colloid of German horse and Interface Study the research group of Caruso proposed a kind of self-assembling method layer by layer (LBL) and obtained the good superpolymer of monodispersity/titanium dioxide core shell-type sub-micron ball, finally obtained A-TiO by high temperature sintering subsequently
2Hollow sub-micron ball (Caruso F, et al., Adv.Mater.2001,13,740).Similarly, the people such as Imhof of Holland are template with the polystyrene spheres, at first obtain PS/TiO by the isopropyl titanate hydrolysis
2The nucleocapsid sub-micron ball, and to obtain rutile content by 600 ℃ of sintering be 10% R-A composite phase titanic oxide hollow ball (Imhof A, Langmuir, 2001,17,3579).Jieshijie Novel Materials Co., Ltd, Shanghai has then developed a kind of inorganic carbon/TiO
2Composite Nano hollow microsphere, its preparation method for synthetic high polymer microsphere template system at first, generate inorganic carbon skeleton, cladding titanium dioxide layer, and obtain inorganic carbon/TiO by sintering
2Composite Nano hollow microsphere (application number: 200410099227.2).Recently, the inventor has been developed mixed solvent method and has been prepared the PS/TiO that monodispersity is good, shell thickness is controlled
2Sub-micron ball.Further, obtained A-TiO by high temperature sintering
2Hollow ball (application number: 200610011885.0).Though by the resulting anatase octahedrite of above method is that main titanium dioxide hollow ball can solve the too big problem of white pigment density, because A-TiO
2Light stability is too poor, often causes the organic dye molecule variable color.Therefore in order better to solve the too poor problem of white pigment stability, pure R-TiO
2The synthetic of hollow sub-micron ball is a great challenge at present.The present invention has reported first by simple high temperature sintering and has obtained the red stone type of monodisperse pure titanium dioxide hollow sub-micron ball.What be worth proposition is by selecting whether pass through hydrothermal treatment consists, can selectively obtaining the fine and close and coarse two types red stone type of the monodisperse pure titanium dioxide hollow sub-micron ball of smooth surface.Shaggy single dispersion, titanium dioxide hollow sub-micron ball have the potential use in the medicament slow release field.Adjusting (550～900 ℃) by sintering temperature can make R type content be adjusted to 100% from 10%.
Summary of the invention
One of purpose of the present invention provides single dispersion, shaggy pure rutile type or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball.
Two of purpose of the present invention provides pure rutile type or the rutile-type and the Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball of single dispersion, smooth surface densification.
Three of purpose of the present invention provides a kind of by A-TiO
2Nano particle coats the sub-micron ball of the formed single dispersion of polystyrene spheres, core/shell structure.
Four of purpose of the present invention provides the preparation method of single dispersion, shaggy pure rutile type or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball.
Five of purpose of the present invention provides the preparation method of pure rutile type or the rutile-type and the Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball of single dispersion, smooth surface densification.
Six of purpose of the present invention provides and a kind ofly just can obtain by A-TiO by simple hydrothermal treatment consists
2Nano particle coats the preparation method of the sub-micron ball of the formed single dispersion of polystyrene spheres, shaggy core/shell structure.
The objective of the invention is to realize by following technical scheme:
By mixed solvent system synthetic polystyrene/titanium dioxide (PS/TiO
2) sub-micron ball; The above-mentioned sub-micron ball of hydrothermal treatment consists obtains by A-TiO
2Nano particle coats the sub-micron ball of the formed core/shell structure of polystyrene sub-micron ball, and its monodispersity is good; High temperature sintering obtains single dispersion, shaggy pure rutile type (R-) or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball.In addition by direct high temperature sintering PS/TiO
2Sub-micron ball has synthesized pure rutile type or the rutile-type and the Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball of single dispersion, smooth surface densification.
Red stone type of monodisperse pure of the present invention or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball are to be made of rutile-type and Detitanium-ore-type, the surface irregularity of described titanium dioxide hollow sub-micron ball or smooth densification; Wherein, the mass content of the rutile in the titanium dioxide hollow sub-micron ball can be controlled in 10% to 100% scope, can from contain quality be 90% Detitanium-ore-type to adjust to mass content be 100% pure rutile type, form by pure titinium dioxide.
Density 4.26g/cm with solid rutile titanium dioxide
3Compare, the density of titanium dioxide hollow sub-micron ball of the present invention can be reduced to and be about 2.5g/cm
3, even be reduced to and be about 2.1g/cm
3
The particle diameter of described titanium dioxide hollow sub-micron ball can be regulated in 90～600nm scope.
Be used to prepare the red stone type of described shaggy monodisperse pure or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball single of the present invention disperses, the core/shell structure sub-micron ball, be by hydrothermal method obtain by anatase titanium dioxide (A-TiO
2) the formed list of nano particle coating polystyrene (PS) ball disperses, the core/shell structure sub-micron ball, the particle diameter of its single dispersion, core/shell structure sub-micron ball is 120～750nm, shell is made up of the anatase titanium dioxide nano particle that is of a size of tens nanometers, and preferred shell is made up of the anatase titanium dioxide nano particle that is of a size of 5～50 nanometers.
The preparation method of red stone type of the shaggy monodisperse pure of the present invention or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball, the sub-micron ball that coats the formed single dispersion of polystyrene spheres, core/shell structure with titania nanoparticles is that forerunner's reactant is prepared, and may further comprise the steps:
1). unformed titania nanoparticles is coated polystyrene (PS/TiO
2) ball formedly single disperses, the sub-micron ball of core/shell structure is dispersed in as forerunner's reactant that (concentration range can be 1～50g/L) in the deionized water, magnetic is transferred to (as the tetrafluoroethylene reactor) in the reactor after stirring, and carries out hydrothermal treatment consists at 80～200 ℃; Air naturally cools to room temperature;
2). with the mixed solution centrifugation of step 1), after the vacuum-drying of gained precipitation, obtain by anatase titanium dioxide (A-TiO
2) the formed list of nano particle coating polystyrene (PS) ball disperses, the core/shell structure sub-micron ball;
3). with step 2) obtain single disperse, core/shell structure sub-micron ball sintering (in the air atmosphere tube furnace) in 550～900 ℃ air atmosphere, remove the polystyrene ball template, simultaneously Detitanium-ore-type (metastable facies pattern) titanium dioxide is converted into the high rutile-type of chemical stability (stablizing facies pattern) titanium dioxide, has obtained single dispersion, shaggy pure rutile type or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball.
The described unformed titania nanoparticles of step 1) coats polystyrene (PS/TiO
2) the formed sub-micron ball of ball in reactor, under 80～200 ℃, carry out hydrothermal treatment consists, be to make unformed titania nanoparticles be converted into Detitanium-ore-type TiO
2Nano particle; Detitanium-ore-type TiO as shell
2Nanoparticle size can change by hydrothermal condition.
Described is 1～3 day 80～200 ℃ of times of carrying out hydrothermal treatment consists.
Described in 550～900 ℃ air atmosphere the agglomerating time be 1～6 hour, be that single that regulation and control obtain disperses, the mass content of the rutile-type in shaggy pure rutile type or rutile-type and the Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball is 10% to 100%.Can be that to adjust to mass content be 100% pure rutile type for 90% Detitanium-ore-type from containing quality.
The preparation method of red stone type of the monodisperse pure of smooth surface densification of the present invention or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball coats polystyrene (PS/TiO with unformed titania nanoparticles
2) ball formedly single disperses, the sub-micron ball of core/shell structure is as forerunner's reactant, direct sintering (in the air atmosphere tube furnace) in 550～900 ℃ air atmosphere, remove the polystyrene ball template, obtained pure rutile type or the rutile-type and the Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball of single dispersion, smooth surface densification.
Described with unformed titania nanoparticles coating polystyrene (PS/TiO
2) ball formedly single disperses, the sub-micron ball of core/shell structure is as precursor, directly sintering in 550～900 ℃ air atmosphere when removing the polystyrene ball template, can make most of Detitanium-ore-type TiO
2Be converted into rutile TiO
2The mass content of rutile can adjust to 100% from 10%, and hollow structure still can keep.
Described in 550～900 ℃ air atmosphere the agglomerating time be 1～6 hour, be that single that regulation and control obtain disperses, the pure rutile type of smooth surface densification or the mass content of the rutile in rutile-type and the Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball be 10% to 100%.Can be that to adjust to mass content be 100% pure rutile type for 90% Detitanium-ore-type from containing quality.
The used unformed titania nanoparticles of the present invention coats polystyrene (PS/TiO
2) the formed list of ball disperses, the sub-micron ball forerunner reactant of core/shell structure is to adopt the mixed solvent method preparation, as patent of invention (application number: 200610011885.0).The TiO that forms by titania nanoparticles
2Shell thickness can be regulated and control to 65nm from 20nm; That is, if be of a size of 80～620nm, PS/TiO as the PS ball of template
2The size of nuclear/shell ball can be regulated and control to 750nm from 120nm.The synthetic A-TiO of institute
2A-TiO in the sub-micron ball of the formed single dispersion of nano particle coating PS ball, core/shell structure
2Particle size can be by changing the hydrothermal condition regulation and control; Rutile content in single dispersion, surface irregularity or smooth densification, rutile-type and the Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball can be regulated by changing sintering temperature, even can obtain pure rutile type titanium dioxide hollow sub-micron ball.
Method mild condition of the present invention, preparation process is simple, easily repeats operation, and product controllable size easily.Rutile-type of the present invention or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball are a kind of high function fine inorganic body materials, are a kind of important chemical and environmentally conscious materials.Can be widely used in fields such as coating, transmitter, chemical fibre, printing ink, function ceramics, Electronic Paper, medicament slow release.
The preparation method of single dispersion of the present invention, smooth surface densification or coarse pure rutile type or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball possesses:
1. reaction conditions gentleness, forerunner's reactant are synthetic easily, and operation is simple, easy to utilize.
2. institute's synthetic is by A-TiO
2Nano particle coats the A-TiO in the formed single dispersion of PS ball, the core/shell structure sub-micron ball
2Nanoparticle size can be by changing the hydrothermal condition regulation and control.
3. by adjusting the adjustable TiO of sintering temperature
2Rutile content in the hollow sub-micron ball, even can obtain pure rutile type TiO
2The hollow sub-micron ball.
Through after the hydrothermal treatment consists again high temperature sintering can obtain the adjustable titanium dioxide hollow sub-micron ball of shaggy rutile content, can obtain the adjustable titanium dioxide hollow sub-micron ball of rutile content of smooth surface densification without hydrothermal treatment consists.
Description of drawings
Fig. 1. the embodiment of the invention 1 by anatase titanium dioxide (A-TiO
2) the formed list of nano particle coating polystyrene spheres disperses, the X-ray powder diffraction pattern (XRD) of the sub-micron ball of core/shell structure.
Fig. 2. the embodiment of the invention 1 by anatase titanium dioxide (A-TiO
2) the formed list of nano particle coating polystyrene spheres disperses, the scanning electron microscope microphotograph (SEM) of the sub-micron ball of core/shell structure.
Fig. 3. the pure rutile type TiO of single dispersion, surface irregularity or the smooth densification of the embodiment of the invention 1
2The XRD of hollow sub-micron ball.
Fig. 4. single dispersion of the embodiment of the invention 1, shaggy pure rutile type TiO
2The SEM of hollow sub-micron ball.
Fig. 5. single dispersion of the embodiment of the invention 2, the pure rutile type TiO of smooth surface densification
2The SEM of hollow sub-micron ball.
Embodiment
Embodiment 1
(1). adopt application for a patent for invention number: the method in 200610011885.0 has prepared single dispersion PS/TiO
2Sub-micron ball, size is about 350nm.Nuclear is the PS ball of 240nm, the TiO that is made up of titania nanoparticles
2Shell thickness is 55nm.
(2). the colloidal solid of the polystyrene microsphere surface cladding titanium dioxide that step (1) is obtained is distributed in the deionized water, concentration range can be at 1～50g/L, magnetic is transferred to it in hydrothermal reaction kettle after stirring, reacted 24 hours down at 80 ℃, its shell is made up of anatase structured titania nanoparticles.Centrifugation, dry gained sample are also preserved in order to next step operation.Its crystalline structure and pattern such as Fig. 1, shown in 2, shell is made up of the anatase structured titania nanoparticles that is of a size of 5～50 nanometers, and kernel is the PS ball.Because unformed titanium dioxide becomes the nano particle of 5～50 nano-scales by crystallization, has the space between the particle, so the titanium dioxide shell thickness increases to about 75nm by former 55nm, and the size of whole sub-micron ball is about 390nm.
(3). step (2) gained sample is placed in the tube furnace 900 ℃ of sintering 2 hours, cool to room temperature.Its crystalline structure and pattern such as Fig. 3 are shown in 4.As shown in Figure 3, the gained sample is the pure rutile type, does not contain other impurity.The gained sample is single dispersion, shaggy titanium dioxide hollow sub-micron ball as shown in Figure 4.The size of titanium dioxide hollow sub-micron ball narrows down to and is about 345nm, and the rutile titanium dioxide nano particle that is about 35nm by size is formed shell, and shell thickness is about 55nm, and inner cavity size is about 235nm.The gained list disperses, the density of shaggy titanium dioxide hollow sub-micron ball is about 2.1g/cm
3
Embodiment 2
(1). adopt application for a patent for invention number: the method in 200610011885.0 has prepared single dispersion PS/TiO
2Sub-micron ball.
(2). with step (1) gained sample 900 ℃ of sintering 2 hours in tube furnace, cool to room temperature.The gained sample is the titanium dioxide hollow sub-micron ball of single dispersion, smooth surface densification, and the rutile mass content is 100%.Its pattern is (little figure is the partial enlarged drawing of the titanium dioxide hollow sub-micron ball of gained smooth surface densification) as shown in Figure 5.The size of whole titanium dioxide hollow sub-micron ball is about 315nm, and inner cavity size is about 235nm.The density of titanium dioxide hollow sub-micron ball is about 2.5g/cm
3
Embodiment 3
(1). adopt application for a patent for invention number: the method in 200610011885.0 has prepared single dispersion PS/TiO
2Sub-micron ball.
(2). with step (1) gained sample 700 ℃ of sintering 4 hours in tube furnace, cool to room temperature.The gained sample is the titanium dioxide hollow sub-micron ball of single dispersion, smooth surface densification, and the rutile mass content is 50%.
Embodiment 4
(1). adopt application for a patent for invention number: the method in 200610011885.0 has prepared single dispersion PS/TiO
2Sub-micron ball.
(2). with step (1) gained sample 550 ℃ of sintering 6 hours in tube furnace, cool to room temperature.The gained sample is the titanium dioxide hollow sub-micron ball of single dispersion, smooth surface densification, and the rutile mass content is 10%.
Embodiment 5
(1). adopt application for a patent for invention number: the method in 200610011885.0 has prepared single dispersion PS/TiO
2Sub-micron ball is of a size of 120nm.Nuclear is the PS ball of 80nm, the TiO that is made up of titania nanoparticles
2Shell thickness is 20nm.
(2). step (1) gained sample is placed in the tube furnace 800 ℃ of sintering 2 hours, cool to room temperature.The gained sample is the pure rutile type titanium dioxide hollow sub-micron ball of single dispersion, smooth surface densification, does not contain other impurity, and the rutile mass content is 100%, and size is about 90nm.
Embodiment 6
(1). adopt application for a patent for invention number: the method in 200610011885.0 has prepared single dispersion PS/TiO
2Sub-micron ball is of a size of 730nm.Nuclear is the PS ball of 620nm, the TiO that is made up of titania nanoparticles
2Shell thickness is 55nm.
(2). step (1) gained sample is placed in the tube furnace 900 ℃ of sintering 2 hours, cool to room temperature.The gained sample is the pure rutile type titanium dioxide hollow sub-micron ball of single dispersion, smooth surface densification, does not contain other impurity, and the rutile mass content is 100%, and size is about 600nm.
Claims (5)
- One kind single disperse, the preparation method of pure rutile type or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball, the sub-micron ball that coats the formed single dispersion of polystyrene spheres, core/shell structure with titania nanoparticles is forerunner's reactant, be prepared red stone type of shaggy monodisperse pure or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball, it is characterized in that: described method may further comprise the steps:1). the sub-micron ball that unformed titania nanoparticles is coated the formed single dispersion of polystyrene spheres, core/shell structure is dispersed in the deionized water as forerunner's reactant, and magnetic is transferred in the reactor after stirring, and carries out hydrothermal treatment consists at 80～200 ℃; Air naturally cools to room temperature;2). with the mixed solution centrifugation of step 1), after the vacuum-drying of gained precipitation, obtain coating the formed single dispersion of polystyrene spheres, core/shell structure sub-micron ball by the anatase titanium dioxide nano particle;3). with step 2) obtain single disperse, core/shell structure sub-micron ball sintering in 550～900 ℃ air atmosphere, remove the polystyrene ball template, simultaneously anatase titanium dioxide is converted into the high rutile titanium dioxide of chemical stability, has obtained single dispersion, shaggy pure rutile type or rutile-type and Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball;Described titanium dioxide hollow sub-micron ball is to be made of rutile-type and Detitanium-ore-type, the surface irregularity of described titanium dioxide hollow sub-micron ball; Wherein, the mass content of the rutile in the titanium dioxide hollow sub-micron ball is controlled in 10% to 100% scope, can be that to adjust to mass content be 100% pure rutile type for 90% Detitanium-ore-type from containing quality.
- 2. method according to claim 1 is characterized in that: described is 1～3 day 80～200 ℃ of times of carrying out hydrothermal treatment consists.
- 3. method according to claim 1, it is characterized in that: described in 550～900 ℃ air atmosphere the agglomerating time be 1～6 hour, be 10% to 100% with the mass content of the rutile in regulation and control single disperseing of obtaining, shaggy pure rutile type or rutile-type and the Detitanium-ore-type composite phase titanic oxide hollow sub-micron ball.
- 4. method according to claim 1 is characterized in that: step 1) is described will single disperse, the sub-micron ball of core/shell structure is dispersed in concentration range in the deionized water at 1～50g/L as forerunner's reactant.
- 5. method according to claim 1 is characterized in that: the particle diameter of described titanium dioxide hollow sub-micron ball is 90～600nm.
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| CN102502807A (en) * | 2011-10-27 | 2012-06-20 | 天津大学 | White hollow titanium dioxide microsphere and preparation method thereof |
| KR101785268B1 (en) * | 2013-12-10 | 2017-10-16 | 삼성에스디아이 주식회사 | Negative active material and lithium battery including the material, and method for manufacturing the material |
| CN104961157A (en) * | 2015-07-03 | 2015-10-07 | 燕山大学 | Synthetic method of rutile TiO2 |
| CN105078879B (en) * | 2015-09-06 | 2017-10-27 | 江苏大学 | A kind of preparation method of Tegafur sustained release agent |
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| CN1478725A (en) * | 2003-01-13 | 2004-03-03 | 复旦大学 | Preparation method of crystal phase controllable titanium dioxide nanometer crystal |
| CN1824382A (en) * | 2006-01-16 | 2006-08-30 | 徐志兵 | Preparation method of titanium dioxide hollow microsphere |
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| CN1478725A (en) * | 2003-01-13 | 2004-03-03 | 复旦大学 | Preparation method of crystal phase controllable titanium dioxide nanometer crystal |
| CN1824382A (en) * | 2006-01-16 | 2006-08-30 | 徐志兵 | Preparation method of titanium dioxide hollow microsphere |
| CN1834021A (en) * | 2006-04-07 | 2006-09-20 | 浙江工业大学 | Prepn. process of mesic hole hollow ball-shape titania powder |
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