CN1092147C - Process for preparing uniform compound monodispersed nm-class spherical TiO2 particles - Google Patents
Process for preparing uniform compound monodispersed nm-class spherical TiO2 particles Download PDFInfo
- Publication number
- CN1092147C CN1092147C CN 99123760 CN99123760A CN1092147C CN 1092147 C CN1092147 C CN 1092147C CN 99123760 CN99123760 CN 99123760 CN 99123760 A CN99123760 A CN 99123760A CN 1092147 C CN1092147 C CN 1092147C
- Authority
- CN
- China
- Prior art keywords
- mol
- molar concentration
- particles
- volumetric molar
- original volume
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention relates to a preparation method of uniform compound monodispersed spherical titanium dioxide particles of which the particle diameters are from 55 to 1400 nm. First, silicon dioxide particles are dispersed into a polar organic solvent by ultrasonic sound or stir; the proportion of the weight of the silicon dioxide particles to the volume of the solvent is from 3 to 100 g/l; second, water and/or ammonia water is added to the solution; and third, titanate is added to the solution to cause the initial volume molarity of the mixed ammonia to be from 0.001 to 1 mol/l, the initial volume molarity of the water is from 0.01 to 3 mol/l and the initial volume molarity of the titanate is from 0.005 to 0.5 mol/l for reaction for 3 to 48 hours at the temperature of 25 to 45 DEG C to obtain the uniform compound monodispersed spherical nanometer titanium dioxide particles. The particles obtained by the present invention have high purity and good dispersancy; the size of the particles can be controlled by reaction conditions.
Description
The invention belongs to the preparation and the applied technical field of the inorganic smooth function nano material of semi-conductor, particularly relate to the preparation method of uniform compound monodispersed nm titanium dioxide granule.
TiO
2The popular name titanium dioxide is a kind of more high function fine inorganic material of studying, and is important pottery, semi-conductor and catalytic material, and nano-TiO
2Have more particular performances such as good weathering resistance, chemical resistance, higher chemical stability, thermostability, nontoxicity, photosensitivity, high dispersive and non-migrating and be widely used in fields such as high grade paint, transmitter, dielectric materials, plastics, printing ink, papermaking, chemical fibre and rubber, for example:
(1) nano-TiO
2Have very important optical property---color reaction, and make its extremely the automobile finish expert favor and become the most high-grade effect pigment in the present age.The auto maker that Ford, Chrysler, Toyota, Mazda etc. are famous uses and contains nano-TiO
2Metal car finish paint, this finish paint is coated in the artistic effect that can reach a kind of very graceful fineness on the automobile, and world car industry car over half is all used the application of metal finish paint, to containing nano-TiO
2Metal flash paint require very big.
(2) because nano-TiO
2Characteristics such as existing visible light penetrativity is strong, and is transparent and nontoxic have excellent ultraviolet shielded effect and peculiar colour effect again, available its preparation sunscreen skincare product, and be added in the food product packing film, can make the food matter that remains unchanged for a long period of time, than organic additive obvious superiority is arranged.
(3) nano-TiO
2The specific surface atomicity sharply increases, and the reactive behavior height is so can be used as light-sensitive catalyst, sorbent material.
(4) nano-TiO
2Fusing point is than general T iO
2Low, and uniform particles, can reach tight filling, so can be as good fine ceramics sintering aid.
In addition, nano-TiO
2Can be as the additive of the strengthening agent of the tinting material of the nucleus agent of special glass, resin printing ink, silicon rubber, solid lubricant, matting agent, catalyzer etc.Nano-TiO
2Specific function and purposes and more than these, still among research and development constantly.
Existing in the world at present company more than 10 is at development and production superfine Ti O
2, and Japanese firm is in the majority, its production method mainly is a chlorination process.Chlorination process is with TiCl
4Make superfine Ti O with the oxygen reaction
2But chlorination process needs the raw material of high-grade, and its price just becomes the factor of restriction development.And China is in the early stage of development of titanium dioxide, and production and technology do not break away from the primary stage as yet, do not form scale operation.At present the China's titanium white powder mainly adopts sulfuric acid process, and the kind of product is few, and retaining is time low, and whiteness is bad, mixed crystal, and tinting strength is bad, and granularity is poor, and the production cost height can't satisfy the needs of domestic market and needs to rely on import.The report of this respect is referring to the article " technological transformation of opinion China sulfate process titanium dioxide factory " of 1997 the 6th phases " coatings industry " magazine 19-20 page or leaf.
TiO
2Particle is during as the pigment of excellence and some special purposes, the just particulate outside surface that reality can be utilized and play a role, the kernel of particle then not performance effect should be arranged, the therefore TiO that exists with interior kernel form
2The cost height is actually a kind of huge waste of resource.People actively seek the way that addresses this problem for many years, so the production technology of bag nuclear titanium dioxide pigment occurred.The kernel of existing bag nuclear titanium white is generally used lime carbonate, kaolin, mica etc.Its production method is physics method and chemical method and chemical physics synthetic method.Yet these methods all exist coating not exclusively, and the excessive use meeting of coating is to TiO
2Performance produce negative shortcomings such as influence, and the quality of inner nuclear material and the uneven problem of size-grade distribution that coats titanium white be the key issue of producing bag nuclear titanium white always, and the report of this respect is referring to the article " know-why and developing direction that bag nuclear titanium dioxide pigment is produced " of 1997 the 9th phases " coatings industry " magazine 1-3 page or leaf.
In addition, prepare TiO with the metal alkoxide hydrolysis method
2Energy consumption is low, the product purity height, but particle diameter is difficult to control, and repeatability is difficult to grasp, and is easy to reunite, and is difficult for making the controlled TiO that singly is uniformly dispersed of particle diameter simultaneously
2Particle.This respect content is referring to " Journal of Inorganic Materials " nineteen ninety-five the 10th volume, and " alkoxide hydrolysis prepares TiO to the article of the 4th phase
2Nano-powder ".
The objective of the invention is to overcome the shortcoming of above the whole bag of tricks, a kind of method for preparing purity height, single dispersion, narrow diameter distribution, uniform particles, composite nano titanium dioxide spheroidal particle that the particle diameter controlled range is big is provided.Adopt method of the present invention can prepare singly the be uniformly dispersed nm-class spherical TiO 2 particles of particle diameter at 55～1400nm.
The objective of the invention is to be achieved through the following technical solutions:
Prepare composite Nano TiO with the metal alkoxide hydrolysis method
2Even monodisperse sphere type particle, this particle are at single 50～1300 nanometer spherical SiO of dispersion as kernel
2Coat last layer desired thickness (5～200nm) TiO on the particle
2, make former SiO
2Particle has the character of titanium dioxide granule.
Concrete preparation method is as follows:
With silica dioxide granule with ultrasonic or dispersed with stirring in polar organic solvent, wherein the particle diameter of silica dioxide granule is 50～1300nm, is preferably 50～950nm, the volume ratio of its weight and solvent is 3～100 grams per liters, is preferably 3～50 grams per liters; In above-mentioned solution, add entry and/or ammoniacal liquor again, add titanic acid ester [Ti (OR) then
4], making the original volume volumetric molar concentration of mixed ammonia for a short time is 0.001～1 mol, is preferably 0.001～0.5 mol; The original volume volumetric molar concentration of water is 0.01～3 mol, is preferably 0.015～2 mol; The original volume volumetric molar concentration of titanic acid ester is 0.005～0.5 mol, be preferably 0.005～0.3 mol, reacted 3～48 hours down, obtain oyster white or white opacity solution at 25～45 ℃, centrifugation again, obtain uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter is band glossy white precipitate at 55～1400nm, the vacuum-drying of gained precipitation, or under 450-800 ℃, roast thermal treatment 0.5～1 hour obtains the titanium dioxide powder of rutile-type or anatase titanium dioxide.
Wherein said titanic acid ester [Ti (OR)
4] in R be-C
nH
2n+1, n=2～4; Described polar organic solvent is in the mixed solvent of any solvent in dehydrated alcohol, acetone, acetonitrile, Virahol, ethylene glycol or ethanol and acetone, acetonitrile, Virahol and the ethylene glycol, and its blended volume ratio is 1: 1～5: 1.
Described silica dioxide granule can commercially availablely obtain or adopt the hydrolysis method preparation of Stober to obtain, this method is rolled up the 62nd～69 page article (Werner Stober referring to " colloidal interface science magazine " nineteen sixty-eight the 26th, Arthur FinkandErnst Bohn Controlled Growth of Monodisperse Silica Spheres in the Micron Size Range, Journal of Colloid and Interface Science 26,6269 (1968)), the single SiO that disperses of the preparation of hydrolysis silicon ester in alcohol-ammonia medium of people such as Stober proposition
2Method, become people and studied the method that generally adopts when monodisperse system forms mechanism, be characterized in, be easy to select within the specific limits synthetic required particle grain size.Among the present invention it has been carried out modification, concrete preparation method is as follows:
With ammonia, water and silicon ester [Si (OR)
4] be added in solvent such as the alcohol, making the original volume volumetric molar concentration of mixing back ammonia is 0.5～9 mol, is preferably 0.5～7 mol; The original volume volumetric molar concentration of water is 1～20 mol, is preferably 1～15 mol; Silicon ester [Si (OR)
4] the original volume volumetric molar concentration be 0.01～1.5 mol, be preferably 0.1～1.0 mol; The molarity of the alcoholic solution of silicon ester determines that according to the size of desired silicon dioxide sub-micron grade particles grain diameter increases with the increase of used silicon ester consumption usually.Above-mentioned mixing solutions is at room temperature stirred down reaction 0.5～24 hour, obtain turbid solution; With this turbid solution centrifugation, obtain white depositions silicon-dioxide then, precipitation of silica with small amount of ethanol washing 1～2 time, is finally obtained SiO
2Particle, its particle diameter be in 50～1300 nanometers, preferred 50～950 nanometers, last SiO
2Particle can leave in ethanol, acetone, butanols, Virahol or the ethylene glycol solvent; Or deposit in the solution of water and ammonia; Or vacuum or seasoning preservation.
Wherein said silicon ester [Si (OR)
4] in R be-C
nH
2n+1, n=1～5 are preferably positive tetraethyl orthosilicate [Si (OC
2H
5)
4], solvent alcohol is ethanol, butanols or Virahol.
Description of drawings:
The composite titanium dioxide bead electromicroscopic photograph of Fig. 1-embodiments of the invention 1
Fig. 2-embodiments of the invention 2 composite titanium dioxide bead electromicroscopic photographs
Fig. 3-embodiments of the invention 3 composite titanium dioxide bead electromicroscopic photographs
Effect of the present invention and advantage:
The SiO that adopts method of the present invention to obtain2Particle uniform particles, the single dispersion are such as accompanying drawing 1, accompanying drawing 2 and attached Shown in Figure 3; But the coverage degree to each particle is measured, and the titanium elements that coats on each particle reaches 4～55 % (weight). The weight of silicon and titanium elements content in the single titanium dioxide granule of gained among embodiment 1 and the embodiment 6 Amount percentage sees Table 1:
Table 1
| Element | % by weight | Deviation | |
| Embodiment 1 | Si | 95.72 | 0.363 |
| Ti | 4.28 | 0.08 | |
| Embodiment 6 | Si | 53.52 | 0.597 |
| Ti | 46.48 | 0.576 |
Hydrolyze method of the present invention not only energy consumption is low, the product purity height, evenly, good dispersion, and the size of particle not only can be by preparing in advance kernel dispersed nano spherical SiO2The reaction condition of particle is controlled, and also can pass through TiO2Coating layer thickness is controlled.
The present invention prepares composite Ti O2Method simple, be easy to apply. By with the concentration of esters of silicon acis and The proportioning of water, ammonia is controlled the size of silica dioxide granule particle diameter. By coming with the concentration of titanate esters and the proportioning of water Control the coating layer thickness of titanium dioxide, be easier to make the titanium dioxide of nanoscale monodisperse spherical. With comparatively inexpensive Esters of silicon acis prepare nanometer silicon dioxide particle, prepare monodispersed titanium dioxide with silica dioxide granule as kernel again The method of titanium is very economical and superior. Solvent for use is inexpensive, be easy to get, and safety is recyclable.
What the method was significantly different from the past preparation method is that in the present invention, the preparation of titania nanoparticles is in the spherical SiO that singly is uniformly dispersed as kernel2Evenly apply last layer TiO on the particle2, make particle have dioxy Change the character of titanium.
Purposes of the present invention: product purpose of the present invention is extensive, be high function fine inorganic material, important pottery, Semiconductor and catalysis material are widely used in coating, sensor, dielectric material, plastics, printing ink, papermaking, change The fields such as fibre, rubber.
The present invention is further described by the following embodiment:
Embodiment 1
With ammonia, water and tetraethyl silicate [Si (OC
2H
5)
4] be added in the etoh solvent, making the original volume volumetric molar concentration of mixing back ammonia is 3 mol, and the original volume volumetric molar concentration of water is 7 mol, and the original volume volumetric molar concentration of tetraethyl silicate is 0.25 mol, above-mentioned mixing solutions is at room temperature stirred down reaction 24 hours, obtain turbid solution; With this turbid solution centrifugation, obtain the silicon-dioxide white precipitate then, precipitation of silica with small amount of ethanol washing 2 times, is finally obtained SiO
2Particle, its particle diameter be in 320 nanometers, last SiO
2Particle can leave in the ethanol; Used solvent is recyclable.
50 gram silica dioxide granules are risen in the dehydrated alcohol with dispersed with stirring to 1; In above-mentioned solution, add entry and 25% ammoniacal liquor again, add tetrabutyl titanate [Ti (OC then
4H
9)
4], the original volume volumetric molar concentration that makes mixed ammonia is 0.01mol/L, and the original volume volumetric molar concentration of water is 0.06mol/L, and the original volume volumetric molar concentration of tetrabutyl titanate is 0.015mol/L, reacted 12 hours down at 35 ℃, obtain white opacity solution, centrifugation again obtains being with the glossy white precipitate, the vacuum-drying of gained precipitation, obtain uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 8 nanometers of thickness in 328 nanometers.See accompanying drawing 1.
Embodiment 2
The 35 gram silica dioxide granules that obtain among the embodiment 1 are distributed in 1 liter of dehydrated alcohol again with stirring; In above-mentioned solution, add 25% ammoniacal liquor again, add tetrabutyl titanate [Ti (OC then
4H
9)
4], the original volume volumetric molar concentration that makes mixed water is 0.1mol/L, the original volume volumetric molar concentration of tetrabutyl titanate is 0.03mol/L, reacts 12 hours down at 35 ℃, obtains oyster white or white opacity solution, centrifugation again, obtain being with the glossy white precipitate, the vacuum-drying of gained precipitation obtains uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 30 nanometers of thickness in 352 nanometers.See accompanying drawing 2.
Embodiment 3
With ammonia, water and positive tetraethyl orthosilicate [Si (OC
2H
5)
4] be added in the etoh solvent, making the original volume volumetric molar concentration of mixing back ammonia is 4 mol, the original volume volumetric molar concentration of water is 11 mol, the original volume volumetric molar concentration of positive tetraethyl orthosilicate is 0.5 mol, above-mentioned mixing solutions is at room temperature stirred down reaction 8 hours, obtain turbid solution; With this turbid solution centrifugation, obtain the silicon-dioxide white precipitate then, precipitation of silica with small amount of ethanol washing 1 time, is finally obtained SiO
2Particle, its particle diameter be in 580 nanometers, last SiO
2The particle seasoning is preserved.
30 gram silica dioxide granules are risen in ethanol and the isopropyl alcohol mixed solvent with dispersed with stirring to 1; The volume ratio of ethanol and Virahol is 1: 1, adds entry again in above-mentioned solution, adds isopropyl titanate [Ti (i-OC then
3H
7)
4], the original volume volumetric molar concentration that makes mixed water is 0.4mol/L, isopropyl titanate [Ti (i-OC
3H
7)
4] the original volume volumetric molar concentration be 0.09mol/L, reacted 4 hours down at 45 ℃, obtain oyster white or white opacity solution, centrifugation again, obtain being with the glossy white precipitate, the vacuum-drying of gained precipitation obtains uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 70 nanometers of thickness in 650 nanometers.See accompanying drawing 3.Sintering carries out half an hour at 750 ℃, obtains the titanium dioxide powder of rutile-type.
Embodiment 4
In the commercially available mixed solvent of 5 gram silica dioxide granules (particle diameter 500 nanometers) with ultra-sonic dispersion to 200 milliliter ethanol and acetone; The volume ratio of ethanol and acetone is 7: 3, adds entry again in above-mentioned solution, adds tetraethyl titanate [Ti (OC then
2H
5)
4], making the original volume volumetric molar concentration of mixing back water is 0.45mol/L, the original volume volumetric molar concentration of tetraethyl titanate is 0.11mol/L, reacts 24 hours down at 45 ℃, obtains white opacity solution, centrifugation again, obtain being with the glossy white precipitate, the vacuum-drying of gained precipitation obtains uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 55 nanometers of thickness in 555 nanometers.
Embodiment 5
With ammonia, water and positive tetraethyl orthosilicate [Si (OC
2H
5)
4] be added in the etoh solvent, making the original volume volumetric molar concentration of mixing back ammonia is 0.8 mol, the original volume volumetric molar concentration of water is 1.9 mol, the original volume volumetric molar concentration of tetraethyl silicate is 0.22 mol, above-mentioned mixing solutions is at room temperature stirred down reaction 8 hours, obtain turbid solution; With this turbid solution centrifugation, obtain the silicon-dioxide white precipitate then, precipitation of silica with small amount of ethanol washing 2 times, is finally obtained SiO
2Particle, its particle diameter be in 260 nanometers, last SiO
2Particle can leave in the ethanol; Used solvent is recyclable.
20 gram silica dioxide granules are risen in ethanol and acetonitrile (volume ratio 1: the 1) mixing solutions with dispersed with stirring to 1; In above-mentioned mixing solutions, add entry again, add tetraethyl titanate [Ti (OC then
2H
5)
4], the original volume volumetric molar concentration that makes mixed water is 0.1mol/L, the original volume volumetric molar concentration of tetraethyl titanate is 0.02mol/L, reacts 17 hours down at 30 ℃, obtains the oyster white turbid solution, centrifugation again, obtain being with the glossy white precipitate, the vacuum-drying of gained precipitation obtains uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 70 nanometers of thickness in 330 nanometers.Sintering carries out half an hour at 500 ℃, obtains the titanium dioxide powder of anatase titanium dioxide.
Embodiment 6
Will be by the resulting SiO of preparation among the embodiment 5
2Particle 3 grams are in dispersed with stirring to 200 milliliter ethanol and ethylene glycol (volume ratio 3: 1) mixing solutions; In above-mentioned mixing solutions, add ammoniacal liquor again, add tetrabutyl titanate [Ti (OC then
4H
9)
4], the original volume volumetric molar concentration that makes mixed ammonia is 0.5mol/L, and the original volume volumetric molar concentration of water is 1.6mol/L, and the original volume volumetric molar concentration of tetrabutyl titanate is 0.29mol/L, reacted 48 hours down at 35 ℃, obtain white opacity solution, centrifugation again obtains being with the glossy white precipitate, the vacuum-drying of gained precipitation, obtain uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter promptly clads the titanium dioxide granule of about 200 nanometers of thickness in 460 nanometers.
Embodiment 7
With ammonia, water and tetraethyl silicate [Si (OC
2H
5)
4] be added drop-wise in the etoh solvent, making the original volume volumetric molar concentration of mixing back ammonia is 8.7 mol, the original volume volumetric molar concentration of water is 19 mol, the original volume volumetric molar concentration of tetraethyl silicate is 1.5 mol, above-mentioned mixing solutions is at room temperature stirred down reaction 20 hours, obtain turbid solution; With this turbid solution centrifugation, obtain the silicon-dioxide white precipitate then, its particle diameter is in 1280 nanometers, last SiO
2Particle can leave in the ethanol; Used solvent is recyclable.
Above-mentioned silica dioxide granule 80 grams are risen in the dehydrated alcohol with dispersed with stirring to 1; In above-mentioned solution, add entry and 25% ammoniacal liquor again, be added dropwise to tetrabutyl titanate [Ti (OC then
4H
9)
4], the original volume volumetric molar concentration that makes mixed ammonia is 0.92mol/L, the original volume volumetric molar concentration of water is 3.0mol/L, and the original volume volumetric molar concentration of tetrabutyl titanate is 0.5mol/L, reacts 36 hours down at 35 ℃, obtain oyster white or white opacity solution, centrifugation again obtains being with the glossy white precipitate, the vacuum-drying of gained precipitation, obtain uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter is in 1380 nanometers.
Embodiment 8
With ammonia, water and tetraethyl silicate [Si (OC
2H
5)
4] be added in the etoh solvent, making the original volume volumetric molar concentration of mixing back ammonia is 0.5 mol, original volume volumetric molar concentration 2.0 mol of water, the original volume volumetric molar concentration of tetraethyl silicate is 0.18 mol, above-mentioned mixing solutions is at room temperature stirred down reaction 8 hours, obtain the white turbid solution of micro emulsion; SiO
2Particle grain size is in 51 nanometers.
100ml is contained the solution of above-mentioned silica dioxide granule, under agitation add entry again, add tetrabutyl titanate [Ti (OC then
4H
9)
4], the original volume volumetric molar concentration that makes mixed ammonia is 0.5mol/L, the original volume volumetric molar concentration of water is 0.02mol/L, and the original volume volumetric molar concentration of tetrabutyl titanate is 0.0067mol/L/, reacts 12 hours down at 35 ℃, obtain oyster white or white opacity solution, centrifugation again obtains being with the glossy white precipitate, the vacuum-drying of gained precipitation, obtain uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter is in 70 nanometers.
Claims (5)
1. the preparation method of a uniform compound monodispersed nm-class spherical TiO 2 particles, it is characterized in that with silica dioxide granule with ultrasonic or dispersed with stirring in polar organic solvent, the volume ratio of its weight and polar organic solvent is 3～100 grams per liters; In above-mentioned solution, add entry and/or ammoniacal liquor again, add titanic acid ester then, the original volume volumetric molar concentration that makes mixed ammonia is 0.001～1 mol, the original volume volumetric molar concentration of water is 0.01～3 mol, the original volume volumetric molar concentration of titanic acid ester is 0.005～0.5 mol, reacted 3-48 hour down at 25～45 ℃, obtain oyster white or white opacity solution, centrifugation again, obtain being with the glossy white precipitate, be uniform compound monodispersed nm-class spherical TiO 2 particles, particle diameter is in 55～1400 nanometers; The particle diameter of described silica dioxide granule is the 50-1300 nanometer; The molecular formula of described titanic acid ester is Ti (OR)
4, wherein R is-C
nH
2n+1, n=2～4.
2. the preparation method of uniform compound monodispersed nm-class spherical TiO 2 particles as claimed in claim 1, it is characterized in that described white precipitate vacuum-drying, or under 450～800 ℃, roast thermal treatment 0.5～1 hour gets anatase titanium dioxide or rutile titanium dioxide powder.
3. the preparation method of uniform compound monodispersed nm-class spherical TiO 2 particles as claimed in claim 1 is characterized in that the weight of described silica dioxide granule and the volume ratio of polar organic solvent are 3～50 grams per liters; The original volume volumetric molar concentration of described mixed ammonia is 0.001～0.5 mol; The original volume volumetric molar concentration of water is 0.015～2 mol, and the original volume volumetric molar concentration of titanic acid ester is 0.005～0.3 mol.
4. the preparation method of uniform compound monodispersed nm-class spherical TiO 2 particles as claimed in claim 1, it is characterized in that described polar organic solvent be dehydrated alcohol, acetone, acetonitrile, Virahol, ethylene glycol or ethanol with acetone, acetonitrile, Virahol and ethylene glycol in the mixing of any solvent, its blended volume ratio is 1: 1～5: 1.
5. the preparation method of uniform compound monodispersed nm-class spherical TiO 2 particles as claimed in claim 1, the particle diameter that it is characterized in that described silica dioxide granule is 50～950 nanometers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123760 CN1092147C (en) | 1999-11-19 | 1999-11-19 | Process for preparing uniform compound monodispersed nm-class spherical TiO2 particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123760 CN1092147C (en) | 1999-11-19 | 1999-11-19 | Process for preparing uniform compound monodispersed nm-class spherical TiO2 particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1296917A CN1296917A (en) | 2001-05-30 |
| CN1092147C true CN1092147C (en) | 2002-10-09 |
Family
ID=5282968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99123760 Expired - Fee Related CN1092147C (en) | 1999-11-19 | 1999-11-19 | Process for preparing uniform compound monodispersed nm-class spherical TiO2 particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1092147C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296274C (en) * | 2005-03-03 | 2007-01-24 | 武汉理工大学 | Composite microballoon of monodisperse SiO2 and TiO2 and its prepn process |
| CN101319405B (en) * | 2007-06-08 | 2011-05-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Production method of TiO2 nanotube and/or TiO2 nano-whisker |
| CN101549285B (en) * | 2009-05-13 | 2011-02-02 | 西安理工大学 | A method for preparing nano TiO2*/SiO2* photocatalytic material |
| CN101913612A (en) * | 2010-09-01 | 2010-12-15 | 中国石油大学(北京) | Method for preparing micron-sized monodisperse silica microspheres |
| CN103351156B (en) * | 2013-07-05 | 2014-07-16 | 陕西师范大学 | Silicon dioxide-based composite ceramic with near-zero resonance frequency temperature coefficient and preparation method thereof |
| CN106492861B (en) * | 2015-09-08 | 2019-02-19 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method thereof being used to prepare cis-butenedioic anhydride |
| CN105768182A (en) * | 2016-04-19 | 2016-07-20 | 滁州卷烟材料厂 | Tobacco flakes added with grape vine and production method tobacco flakes |
| CN108002432A (en) * | 2017-12-14 | 2018-05-08 | 苏州中科纳福材料科技有限公司 | The preparation method of spherical composite material |
| CN114425313B (en) * | 2020-10-14 | 2023-09-29 | 中国石油化工股份有限公司 | Titanium dioxide-aluminum oxide composite oxide and preparation and application thereof |
-
1999
- 1999-11-19 CN CN 99123760 patent/CN1092147C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1296917A (en) | 2001-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hsu et al. | Paper whiteners: I. Titania coated silica | |
| AU2002239359B2 (en) | Substantially transparent, abrasion-resistant films containing surface-treated nanocrystalline particles | |
| US5846310A (en) | Coated spherical SiO2 particles | |
| US5536448A (en) | Dendrite or asteroidal titanium dioxide micro-particles | |
| US5403513A (en) | Titanium oxide sol and process for preparation thereof | |
| CN1083865C (en) | Plate-like titanium dioxide pigment | |
| CN1198883C (en) | Flaky pigment and its production method | |
| US5248556A (en) | Systhetic whitener pigment | |
| JP5250558B2 (en) | Improved process for the production of zirconia treated titanium dioxide pigments | |
| CN1089101C (en) | Durable pigmentary titanium dioxide and methods of producing the same | |
| JP2010006629A (en) | Titanium dioxide fine particle and method for producing the same | |
| Liang et al. | Mineral-TiO2 composites: Preparation and application in papermaking, paints and plastics | |
| CN1092147C (en) | Process for preparing uniform compound monodispersed nm-class spherical TiO2 particles | |
| CN100503447C (en) | Method for preparing monodispersion ball-shape mesoporous titanium dioxide colloid particles with controllable size and apparance | |
| JP3755852B2 (en) | Coating liquid for forming transparent film having photocatalytic activity and substrate with transparent film | |
| CN1264931C (en) | Spherical zinc oxide and titanium dioxide composite particles with microgranular structure on the surface and preparation method and use thereof | |
| CN108793226B (en) | Method for preparing transparent zinc oxide liquid-phase dispersion by supergravity technology | |
| CN113877563B (en) | Cerium-coated titanium dioxide and preparation method thereof | |
| CN112125335A (en) | Micro-nano titanium dioxide, preparation method and application | |
| JPH06116507A (en) | Iridescent luster pigment | |
| JP4382872B1 (en) | Method for producing titanium oxide particles | |
| CN1286731C (en) | Preparation of single-disperse shperical titanic oxide gel particle with controllable size and appearance | |
| Liu et al. | Preparation and self-assembly of uniform TiO2/SiO2 composite submicrospheres | |
| CN113896232B (en) | Titanium dioxide material and preparation method and application thereof | |
| CN109608658B (en) | Structural color particle and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20021009 Termination date: 20141119 |
|
| EXPY | Termination of patent right or utility model |