CN1903948A - In situ cladding technology of titanium dioxide nano-particle - Google Patents
In situ cladding technology of titanium dioxide nano-particle Download PDFInfo
- Publication number
- CN1903948A CN1903948A CN 200510041257 CN200510041257A CN1903948A CN 1903948 A CN1903948 A CN 1903948A CN 200510041257 CN200510041257 CN 200510041257 CN 200510041257 A CN200510041257 A CN 200510041257A CN 1903948 A CN1903948 A CN 1903948A
- Authority
- CN
- China
- Prior art keywords
- titanium
- nano
- particle
- titanium dioxide
- original position
- 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.)
- Pending
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a surface covering process of nano-grade titanium dioxide particles. It is characterized by that it uses ethylene glycol as organic solvent, makes titanium alcohol salt or inorganic salt of titanium implement hydrolysis reaction to obtain nano-grade titanium dioxide inorganic particles, then adds sodium silicate, aluminium hydroxide or aluminium sulfate, alcohol amine organic dispersing agent into the system so as to obtain TiO2 nano particles, at the same time make surface covering and organic dispersion treatment.
Description
Technical field
The present invention relates to titanium dioxide (TiO
2) surface treatment, relate in particular to nano level TiO
2The surface of particle coats, and is in particular a kind of at formation nano level TiO
2In the time of particle, original position carries out surface coated complete processing, belongs to the inorganic particulate technical field of surface, and is and closely related with the synthetic processing of modified poly ester.
Background technology
Functional superpolymer product is more and more in the prior art, and they by add fine size and even nanometer inorganic in polymkeric substance, make product have some new function mostly.But, the inorganic particulate of fine size, particularly nanometer inorganic, in use as easy as rolling off a log generation is reunited and is influenced its functional embodiment.Growing along with nanotechnology, people also improve constantly the requirement of nano material, in order to demonstrate fully the peculiar performance of nano-scale, must effectively prevent particle agglomeration, improve dispersed.It is a technology that therefore grows up that particle surface coats, and its cardinal principle is with surface additive and particle generation chemical reaction or surface adsorption, thereby changes the configuration of surface of particle, improves the particularly dispersing property of powder of fine particle.
Usually, it is again it to be carried out mechanical dispersion after obtaining nano-powder that nano inoganic particle coats, and carries out the surface then and coats processing.Because nano inoganic particle has high specific surface area, preparation is easy to reunite together after forming nano-powder, just is difficult to make it be dispersed into nano level particle once more by mechanical means and in a single day take place to reunite.Just because of this, Chang Gui inorganic nanoparticles sub-surface method for coating is easy to occur disperseing irregular, the unequal problem of surface coating.
As a kind of important additives in the production of polyester, nano level TiO
2The surface coating technology of inorganic particulate becomes a focus of people's research in recent years.It is reported that since 2003, people such as Liao Dongliang have reported " sol-gel processing " preparation nano-TiO
2Technical study; People such as Xing Xi have introduced the method and the characteristics of nanoparticle surface coating in recent years, comprise sedimentation and surface chemical reaction method, sonochemistry method and nanoparticle self-assembly method etc. in the inorganics coating; Grandson gives the nano-TiO that the rare people of grade has invented a kind of surface-coating aluminum oxide
2The particulate preparation method adopts " sol-gel processing " synthesis nano TiO earlier
2, and then carry out the aluminum oxide coating.
Summary of the invention
The purpose of this invention is to provide a kind of titanium dioxide nano-particle original position cladding process, generate nano level TiO in preparation
2In the time of particle, original position is carried out the surface and is coated, and passes through organic dispersion treatment again, thereby obtaining to avoid reunites between nanoparticle, dispersing property is good, can directly apply to the TiO of production of polyester
2Nanoparticle.
Purpose of the present invention is achieved through the following technical solutions:
Titanium dioxide nano-particle original position cladding process carries out original position and coats after titanium dioxide nano-particle generates, may further comprise the steps---
1. with ethylene glycol as organic solvent, make the inorganic salt generation hydrolysis reaction of titanium alkoxide or titanium, generate the Nano titanium dioxide inorganic particulate;
2. 1. add water glass in the system after the hydrolysis reaction to step, progressively reduce pH value to 6.0～2.0, the formation speed of control silicon-dioxide makes the silicon-dioxide even compact ground sedimentation of generation and is coated on the nano-titania particle surface;
3. increase pH value to 7.0～9.0 gradually, add aluminium hydroxide or Tai-Ace S 150 again in system, regulate pH value in 7.5～11.0 scopes, the formation speed of control aluminium sesquioxide is coated on silica sphere with making the aluminium sesquioxide even compact.
More specifically, in the above-mentioned titanium dioxide nano-particle original position cladding process, 1. step is implemented in accordance with the following methods:
The inorganic salt of titanium alkoxide or titanium are dissolved in ethylene glycol, regulator solution PH is 6.5～3.0, slowly adds de-mineralized water under intense stirring condition, makes the inorganic salt generation hydrolysis reaction of titanium alkoxide or titanium, the control hydrolysis speed of response, thus the Nano titanium dioxide particle formed;
Perhaps, earlier sodium hydroxide is dissolved in ethylene glycol wiring solution-forming A, again with inorganic salt wiring solution-forming B in the middle of oxalic acid is dissolved in ethylene glycol of titanium alkoxide or titanium, under agitation condition, B solution progressively is added drop-wise to A solution, the water molecules that utilizes the reaction of oxalic acid and sodium hydroxide to produce makes the inorganic salt generation hydrolysis reaction of titanium alkoxide or titanium, thereby the speed of the growing amount control hydrolysis reaction of control water, and then obtain the Nano titanium dioxide particle.
Again further, in the above-mentioned titanium dioxide nano-particle original position cladding process, 1. step before hydrolysis reaction, has also added the alcamines organic dispersing agent in the system; The inorganic salt of described titanium alkoxide or titanium are tetrabutyl titanate, titanium ethanolate, isopropyl titanate, titanium tetrachloride, titanium sulfate or titanous oxalate.
The present invention coats processing on the generated in-situ surface of carrying out simultaneously of nano titanium oxide, avoids reuniting between nanoparticle, also the catalytic activity of nano titanium oxide has been carried out deactivation simultaneously." coating back nano-titania particle-ethylene glycol " system that the present invention obtains, dispersing property is good, stability is high, leave standstill and demixing phenomenon can not occur in 72 hours, this system can directly apply to industrialization production of polyester line, realize the effectively compound of inorganic nano-particle and superpolymer, thereby prepare the functional product innovation of high added value such as uvioresistant modified Nano polyester.Therefore, single stage method of the present invention has been finished " TiO
2Nanoparticle generates-→ original position coats-→ disperse to use " etc. a plurality of processes, the manufacturing process of having simplified this series products, the tooling cost of having saved product greatly.
Embodiment
The present invention carries out surface coating, organic dispersion treatment simultaneously in the generated in-situ process of inorganic nano-particle, be applied directly to then in the production process of polyester, form effective complex body of inorganic nano-particle and superpolymer, the realization nanoparticle generates, the surperficial one-step technology that coats, disperses use.Its basic technical scheme is:
The inorganic salt of titanium alkoxide or titanium are dissolved in the ethylene glycol, regulator solution PH is 6.5～3.0, slowly adds de-mineralized water under intense stirring condition, makes the inorganic salt generation hydrolysis reaction of titanium alkoxide or titanium, the control hydrolysis speed of response, thus the Nano titanium dioxide particle formed.Or, earlier sodium hydroxide is dissolved in ethylene glycol wiring solution-forming A, again with inorganic salt wiring solution-forming B in the middle of oxalic acid is dissolved in ethylene glycol of titanium alkoxide or titanium, under agitation condition, B solution progressively is added drop-wise to A solution, the water molecules that utilizes the reaction of oxalic acid and sodium hydroxide to produce makes the inorganic salt generation hydrolysis reaction of titanium alkoxide or titanium, thereby the speed of the growing amount control hydrolysis reaction of control water, and then obtain the Nano titanium dioxide particle.Add silicate behind the hydrolysis reaction, regulate the formation speed of silicon-dioxide, make the silicon-dioxide that generates even compact ground sedimentation to be coated on the nano titanium oxide surface by progressively reducing the system pH value.And then regulate pH value gradually, make PH progressively greater than 7, whole reaction system is under the alkaline condition, under acidic conditions, do not have hydrolysis completely the titanium alkoxide hydrolysis can further take place.At this moment, in system, add amphoteric aluminium hydroxide or Tai-Ace S 150 again,, make aluminium sesquioxide can be coated on silica particle surface even compact by regulating the formation speed of pH value control aluminium sesquioxide.Add organic dispersing agent at last again, the probability of reunion takes place in nano titanium oxide in the further minimizing system.Like this, generated in-situ nano titanium oxide inorganic particle surface just evenly coats and has gone up silicon-dioxide and aluminium sesquioxide, can effectively increase sterically hinderedly, has eliminated the photocatalytic activity of nano titanium oxide.Because entire reaction is all carried out in the ethylene glycol solvent system, so carry out with this technology that original position coats, dispersive nano titanium oxide inorganic particle can single stage method use in polyester (PET) production process, realize the effectively compound of inorganic nano-particle and superpolymer, thereby prepare the modified Nano polyester product innovation of high added value.
Below in conjunction with specific embodiment technical solution of the present invention is described further.These examples only are some exemplary applications, and the claimed interest field of the present invention is not limited.
Embodiment one:
, as solvent the 2.0g tetrabutyl titanate is dissolved in the 300g ethylene glycol with ethylene glycol (EG), regulator solution PH is 6.5～3.0, slowly adds entry under intense stirring condition, and the control hydrolysis speed of response is to form the Nano titanium dioxide inorganic particulate.Hydrolysis reaction back fully adds water glass, progressively reduces pH value to 6.0～2.0, and the formation speed of control silicon-dioxide makes the silicon-dioxide even compact ground sedimentation of generation be coated on the nano titanium oxide surface.And then increase pH value gradually, making PH is 7.0～9.0, whole reaction system is under the alkaline condition, under acidic conditions, do not have hydrolysis completely tetrabutyl titanate hydrolysis can further take place.At this moment, add amphoteric aluminium hydroxide or Tai-Ace S 150 again in system, regulate pH value in 7.5～11.0 scopes, the formation speed of control aluminium sesquioxide is coated on silica sphere with making the aluminium sesquioxide even compact.After add the trolamine organic dispersing agent again, add-on is the nano-TiO that the said hydrolyzed reaction process generates
20.2～0.6% of mass content.
Above-mentioned system leaves standstill 72 hours no demixing phenomenons and occurs.This system moves into esterification and the polycondensation process that participates in polyester in the reactor of PET full scale plant in proportion, obtains the titanium dioxide weight content and be 0.5 ‰～3% inorganic nano particle modified polyester product.Practical application and detection show that this nano-modified polyester has superior performances such as uvioresistant.
Embodiment two:
, as solvent the 1.2g titanium tetrachloride is dissolved in the 300g ethylene glycol with ethylene glycol (EG), regulator solution PH is 6.5～3.0, slowly adds entry under intense stirring condition, and the control hydrolysis speed of response is to form the Nano titanium dioxide inorganic particulate.Hydrolysis reaction back fully adds water glass, progressively reduces pH value to 6.0～2.0, and the formation speed of control silicon-dioxide makes the silicon-dioxide even compact ground sedimentation of generation be coated on the nano titanium oxide surface.And then increase pH value gradually, making PH is 7.0～9.0, whole reaction system is under the alkaline condition, under acidic conditions, do not have hydrolysis completely tetrabutyl titanate hydrolysis can further take place.At this moment, add amphoteric aluminium hydroxide or Tai-Ace S 150 again in system, regulate pH value in 7.5～11.0 scopes, the formation speed of control aluminium sesquioxide is coated on silica sphere with making the aluminium sesquioxide even compact.After add the trolamine organic dispersing agent again, add-on is the nano-TiO that the said hydrolyzed reaction process generates
20.2～0.6% of mass content.
Above-mentioned system leaves standstill 72 hours no demixing phenomenons and occurs.This system moves into esterification and the polycondensation process that participates in polyester in the reactor of PET full scale plant in proportion, obtains the titanium dioxide weight content and be 0.5 ‰～3% inorganic nano particle modified polyester product.Practical application and detection show that this nano-modified polyester has superior performances such as uvioresistant.
Embodiment three:
Earlier 80.0gNaOH is dissolved in the 150.0g ethylene glycol, gets solution A, again 1.8g titanium ethanolate and 100.0g oxalic acid are dissolved in the 150.0g ethylene glycol, obtain solution B.A solution progressively is added drop-wise to B solution in the A solution under stirring condition, and the molecular water that utilizes oxalic acid and NaOH to react to produce makes the titanium ethanolate hydrolysis, thus the hydrolysis rate of the growing amount control titanium ethanolate of control water, and then form nano level TiO
2Inorganic particulate.And then according to the nano-TiO of the correlation step among the embodiment one to generating
2Inorganic particulate carries out surface silicon, aluminium coats.After add the trolamine organic dispersing agent again, add-on is the nano-TiO that the said hydrolyzed reaction process generates
20.2～0.6% of mass content.
At last whole system solution is moved into the esterification, the polycondensation that participate in polyester in the reactor that has dropped into 500g terephthalic acid (PTA), obtain the titanium dioxide weight content and be 0.5 ‰～3% inorganic nano-particle and effective complex body of polyester superpolymer, thereby prepare the nano-modified polyester product innovation of high added value.
Claims (5)
1. titanium dioxide nano-particle original position cladding process carries out original position and coats after titanium dioxide nano-particle generates, and may further comprise the steps:
1. with ethylene glycol as organic solvent, make the inorganic salt generation hydrolysis reaction of titanium alkoxide or titanium, generate the Nano titanium dioxide inorganic particulate;
2. 1. add water glass in the system after the hydrolysis reaction to step, progressively reduce pH value to 6.0～2.0, the formation speed of control silicon-dioxide makes the silicon-dioxide even compact ground sedimentation of generation and is coated on the nano-titania particle surface;
3. increase pH value to 7.0～9.0 gradually, add aluminium hydroxide or Tai-Ace S 150 again in system, regulate pH value in 7.5～11.0 scopes, the formation speed of control aluminium sesquioxide is coated on silica sphere with making the aluminium sesquioxide even compact.
2. titanium dioxide nano-particle original position cladding process according to claim 1, it is characterized in that: 1. step is implemented in accordance with the following methods, the inorganic salt of titanium alkoxide or titanium are dissolved in the ethylene glycol, regulator solution PH is 6.5～3.0, under intense stirring condition, slowly add de-mineralized water, make the inorganic salt generation hydrolysis reaction of titanium alkoxide or titanium, the control hydrolysis speed of response, thus form the Nano titanium dioxide particle.
3. titanium dioxide nano-particle original position cladding process according to claim 1, it is characterized in that: 1. step is implemented in accordance with the following methods, earlier sodium hydroxide is dissolved in ethylene glycol wiring solution-forming A, again with inorganic salt wiring solution-forming B in the middle of oxalic acid is dissolved in ethylene glycol of titanium alkoxide or titanium, under agitation condition, B solution progressively is added drop-wise to A solution, the water molecules that utilizes the reaction of oxalic acid and sodium hydroxide to produce makes the inorganic salt generation hydrolysis reaction of titanium alkoxide or titanium, thereby the speed of the growing amount control hydrolysis reaction of control water, and then obtain the Nano titanium dioxide particle.
4. according to claim 1 or 2 or 3 described titanium dioxide nano-particle original position cladding process, it is characterized in that: 1. step before hydrolysis reaction, has also added the alcamines organic dispersing agent in the system.
5. according to claim 1 or 2 or 3 described titanium dioxide nano-particle original position cladding process, it is characterized in that: the inorganic salt of described titanium alkoxide or titanium are tetrabutyl titanate, titanium ethanolate, isopropyl titanate, titanium tetrachloride, titanium sulfate or titanous oxalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510041257 CN1903948A (en) | 2005-07-29 | 2005-07-29 | In situ cladding technology of titanium dioxide nano-particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510041257 CN1903948A (en) | 2005-07-29 | 2005-07-29 | In situ cladding technology of titanium dioxide nano-particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1903948A true CN1903948A (en) | 2007-01-31 |
Family
ID=37673319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510041257 Pending CN1903948A (en) | 2005-07-29 | 2005-07-29 | In situ cladding technology of titanium dioxide nano-particle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1903948A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328035B (en) * | 2007-06-20 | 2010-09-01 | 中国矿业大学(北京) | Fly ash hollow microsphere surface modified whitening method |
| CN101891972A (en) * | 2010-07-16 | 2010-11-24 | 河北惠尔信新材料有限公司 | Method for producing chemical fiber titanium dioxide by surface coating of common titanium dioxide (TiO2) in solvent phase |
| CN101734714B (en) * | 2008-11-27 | 2012-01-25 | 比亚迪股份有限公司 | Titanium dioxide surface modification method |
| CN101613537B (en) * | 2009-07-31 | 2012-05-30 | 孝感学院 | Preparation method of nano-titanium dioxide coated nano-silicon dioxide |
| CN101684208B (en) * | 2008-09-26 | 2013-05-29 | 比亚迪股份有限公司 | Composite modified titanium dioxide and preparation method thereof |
| CN104027253A (en) * | 2013-03-06 | 2014-09-10 | 广东先导稀材股份有限公司 | Method for one step synthesis of nano-TiO2 for cosmetics |
| CN106674602A (en) * | 2016-12-20 | 2017-05-17 | 广东生益科技股份有限公司 | A preparation method of a coated filler slurry composition, a prepreg, a laminate and a printed circuit board comprising the slurry composition |
| CN106702718A (en) * | 2016-12-05 | 2017-05-24 | 苏州榕绿纳米科技有限公司 | Method for preparing fabric with super wearing resistance, special wettability and anti-ultraviolet function |
| CN106947296A (en) * | 2017-04-26 | 2017-07-14 | 攀钢集团研究院有限公司 | High-weatherability titanium dioxide and preparation method thereof |
| CN107522169A (en) * | 2016-06-22 | 2017-12-29 | 东北林业大学 | A kind of normal temperature prepares pure organic homogeneous precipitation method of nano-oxide |
| CN113881227A (en) * | 2021-11-20 | 2022-01-04 | 彩虹高新材料（莱阳）有限公司 | Ultraviolet-resistant polyether sulfone resin and preparation method thereof |
| CN115010155A (en) * | 2022-04-20 | 2022-09-06 | 兰州石化职业技术学院 | A kind of method for surface modification of carrier silica |
-
2005
- 2005-07-29 CN CN 200510041257 patent/CN1903948A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328035B (en) * | 2007-06-20 | 2010-09-01 | 中国矿业大学(北京) | Fly ash hollow microsphere surface modified whitening method |
| CN101684208B (en) * | 2008-09-26 | 2013-05-29 | 比亚迪股份有限公司 | Composite modified titanium dioxide and preparation method thereof |
| CN101734714B (en) * | 2008-11-27 | 2012-01-25 | 比亚迪股份有限公司 | Titanium dioxide surface modification method |
| CN101613537B (en) * | 2009-07-31 | 2012-05-30 | 孝感学院 | Preparation method of nano-titanium dioxide coated nano-silicon dioxide |
| CN101891972A (en) * | 2010-07-16 | 2010-11-24 | 河北惠尔信新材料有限公司 | Method for producing chemical fiber titanium dioxide by surface coating of common titanium dioxide (TiO2) in solvent phase |
| CN101891972B (en) * | 2010-07-16 | 2013-04-24 | 河北惠尔信新材料有限公司 | Method for producing chemical fiber titanium dioxide by surface coating of common titanium dioxide (TiO2) in solvent phase |
| CN104027253A (en) * | 2013-03-06 | 2014-09-10 | 广东先导稀材股份有限公司 | Method for one step synthesis of nano-TiO2 for cosmetics |
| CN107522169A (en) * | 2016-06-22 | 2017-12-29 | 东北林业大学 | A kind of normal temperature prepares pure organic homogeneous precipitation method of nano-oxide |
| CN106702718A (en) * | 2016-12-05 | 2017-05-24 | 苏州榕绿纳米科技有限公司 | Method for preparing fabric with super wearing resistance, special wettability and anti-ultraviolet function |
| CN106702718B (en) * | 2016-12-05 | 2019-05-14 | 苏州榕绿纳米科技有限公司 | A kind of special wellability uvioresistant function fabric construction method of super abrasive |
| CN106674602A (en) * | 2016-12-20 | 2017-05-17 | 广东生益科技股份有限公司 | A preparation method of a coated filler slurry composition, a prepreg, a laminate and a printed circuit board comprising the slurry composition |
| CN106674602B (en) * | 2016-12-20 | 2019-09-20 | 广东生益科技股份有限公司 | Preparation method of coated filler slurry composition, and prepreg, laminated board and printed circuit board comprising slurry composition |
| CN106947296A (en) * | 2017-04-26 | 2017-07-14 | 攀钢集团研究院有限公司 | High-weatherability titanium dioxide and preparation method thereof |
| CN113881227A (en) * | 2021-11-20 | 2022-01-04 | 彩虹高新材料（莱阳）有限公司 | Ultraviolet-resistant polyether sulfone resin and preparation method thereof |
| CN113881227B (en) * | 2021-11-20 | 2023-11-07 | 彩虹高新材料（莱阳）有限公司 | Ultraviolet-resistant polyether sulfone resin and preparation method thereof |
| CN115010155A (en) * | 2022-04-20 | 2022-09-06 | 兰州石化职业技术学院 | A kind of method for surface modification of carrier silica |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1903948A (en) | In situ cladding technology of titanium dioxide nano-particle | |
| CN101306838B (en) | Preparation method of highly stable neutral mixed crystal nano TiO2 hydrosol | |
| Fajzulin et al. | Nanoparticulate inorganic UV absorbers: a review | |
| CN1295977A (en) | Simple method for preparing titanium dioxide collosol | |
| CN1958198A (en) | Plant reduction method for preparing silver Nano granules and gold Nano granules | |
| CN102886279B (en) | Preparation method for coating metal nanoparticles on surface of nano-titania | |
| CN103880073B (en) | Method for preparing nano titanium dioxide by using micro-reactor and precipitation method | |
| CN102730754A (en) | Preparation method of aqueous nano-TiO2 colloid | |
| CN105540640B (en) | Preparation method of flower-shaped nanometer zinc oxide | |
| CN1226511A (en) | Method for preparing nano sized titanium dioxide powder by alcoholysis from titanic chloride | |
| CN103332737B (en) | Preparation method of titanium dioxide nano-powder | |
| CN108237223A (en) | Hud typed gold-ruthenium-oxide nanocomposite and preparation method thereof | |
| CN105439198B (en) | A kind of preparation method of high ethano/water dispersible nano-titanium dioxide powder | |
| EP2679542A1 (en) | Nanostrutured titania semiconductor material and its production process | |
| Chang et al. | Review of the sol–gel method in preparing nano TiO2 for advanced oxidation process | |
| CN100503447C (en) | Preparation method of monodisperse spherical mesoporous titania colloidal particles with controllable size and shape | |
| CN1264931C (en) | Spherical zinc oxide and titanium dioxide composite particles with particle structures on surfaces, and preparation method and application thereof | |
| CN102618109A (en) | Preparation method and application of ZnO/TiO2 composite powder | |
| CN1078181C (en) | Process for producing nanometre-grade titanic-schorl type titanium dioxide | |
| CN1400169A (en) | Preparation method of titanium oxide nano fibre | |
| Yang et al. | Synthesis of inorganic/organic hybrid-shell antibacterial polyurea microcapsules loaded with Ag/TiO2 nanoparticles | |
| Yan et al. | Microscale spherical TiO2 powder prepared by hydrolysis of TiCl4 solution: Synthesis and kinetics | |
| CN1206163C (en) | Ultrasonic and chemical method for preparing nano crystals of titanium dioxide | |
| CN109529951B (en) | Synthesis method of small-particle-size stably-dispersed nano titanium dioxide | |
| CN1530327A (en) | Preparing method for crystalline nanometer titania material with controllable size |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |