CN1821315A - Polyaniline coated nano TiO2 and poly aniline coated TiO2 whisker and their preparing method - Google Patents
Polyaniline coated nano TiO2 and poly aniline coated TiO2 whisker and their preparing method Download PDFInfo
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- CN1821315A CN1821315A CNA2006100379653A CN200610037965A CN1821315A CN 1821315 A CN1821315 A CN 1821315A CN A2006100379653 A CNA2006100379653 A CN A2006100379653A CN 200610037965 A CN200610037965 A CN 200610037965A CN 1821315 A CN1821315 A CN 1821315A
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- CN
- China
- Prior art keywords
- whisker
- polyaniline
- tio
- nanoparticle
- nanometer tio2
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- 239000002270 dispersing agent Substances 0.000 claims abstract 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 32
- 239000002105 nanoparticle Substances 0.000 claims description 32
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- -1 polyoxyethylene Polymers 0.000 claims description 5
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract 1
- 235000011130 ammonium sulphate Nutrition 0.000 abstract 1
- MMCPOSDMTGQNKG-UJZMCJRSSA-N aniline;hydrochloride Chemical compound Cl.N[14C]1=[14CH][14CH]=[14CH][14CH]=[14CH]1 MMCPOSDMTGQNKG-UJZMCJRSSA-N 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000002114 nanocomposite Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005138 cryopreservation Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The present invention relates to polyaniline coated nanometer TiO2 and polyaniline coated nanometer TiO2 whisker and their preparation process, and belongs to the field of organic-inorganic composite material preparing technology. The materials including nanometer TiO2 or nanometer TiO2 whisker 100 weight portions, aniline hydrochloride 0.1-200 weight portions, dispersant 0.1-50 weight portions, dispersing medium 1000-20000 weight portions and oxidant in the equal equivalent ratio to aniline hydrochloride, are prepared into the polyaniline coated nanometer TiO2 or polyaniline coated nanometer TiO2 whisker through a in-situ chemical oxidizing polymerization process, in which surfactant or dispersant treated nanometer TiO2 or nanometer TiO2 whisker is dispersed in hydrochloric acid to form stable suspension, and aniline hydrochloride is then added via stirring and dropping ammonium sulfate solution. The polyaniline coated nanometer TiO2 and polyaniline coated nanometer TiO2 whisker can absorb ultraviolet ray, visible light and infrared ray.
Description
One, technical field
The invention belongs to a kind of organic-inorganic nanocomposite, particularly the field of conductive polymers-inorganic nano composite material.
Two, background technology
Organic-inorganic nanocomposite is owing to the characteristic of the comprehensive inorganics of energy and organism excellent properties and nano material, and organic-inorganic nanocomposite has very important application prospect in fields such as mechanics, function solenoid, biotechnology.But,, obtain organic-inorganic nanocomposite so be difficult to compound on nanoscale of realization organism and inorganics with traditional blend method because the surfactivity height of nanoparticle reunites easily.
The nano powder that polyacetylene, polypyrrole, Polythiophene and polyaniline etc. have the superpolymer of conductive structure has extraordinary absorbing property.In conductive polymers, polyaniline has higher specific conductivity because of it, and it is good to inhale the ripple wave, good stability, and raw material is cheap, and becomes the conductive polymers that is hopeful to obtain at present practical application most.Inorganic nano-particle and polyaniline are made matrix material, and its photoelectric properties etc. are compared with polyaniline all and are changed to some extent.Because polyaniline-inorganic composite nanoparticles is compound at nano level with organic constituent and inorganic component, the character such as surface effects, volume effect, quantum size effect, macro quanta tunnel effect that not only has nano material, and rigidity, dimensional stability and the thermostability of inorganics and toughness, processibility and the dielectric properties of polymkeric substance blent into one, thereby produce many special performances.
Application for a patent for invention prospectus CN 1446855A and patent of invention specification sheets CN 1096487C have reported electrically conductive polyaniline/manganese dioxide composite material and polyaniline-Fe
3O
4The preparation method of matrix material, but the raw material of oxypolymerization generation polyaniline is not common aniline monomer among the present invention, but aniline hydrochloric acid.Because it is liquid that aniline monomer mostly is, toxicity is bigger, easily crystallization, thus select the aniline hydrochloride crystal for use, little to human body harm; And adopting aniline hydrochloric acid not need to need underpressure distillation, cryopreservation as the liquid phenenyl amine monomers, technology is fairly simple, is suitable for suitability for industrialized production.
Three, summary of the invention
Purpose of the present invention just provides a kind of polyaniline and coats TiO
2Nanoparticle and whisker and relative simple and convenient preparation method thereof.
Polyaniline clad nano TiO of the present invention
2And polyaniline coats TiO
2The parts by weight of each component of whisker are:
TiO
2Nanoparticle or whisker: 100;
Aniline hydrochloric acid: 0.1～200;
Dispersion agent: 0.1～50;
Dispersion medium: 1000～20000;
The equivalence ratio of oxygenant and aniline hydrochloric acid is 1: 1;
1. described dispersion agent is Sodium dodecylbenzene sulfonate or polyoxyethylene glycol;
2. described dispersion medium is the hydrochloric acid soln of 0.2～1.0mol/L;
3. described oxygenant is an ammonium persulphate.
TiO of the present invention
2The median size of nanoparticle is at 10～100nm.The diameter of whisker is 10～400nm, and length is 1～100 μ m.Remove TiO
2Nanoparticle can also be ZnO, Co
3O
4, NiO, MoO
2, WO
3, SiC, Mn-Zn ferrite and carbon nanotube etc. inhale the wavefront modifier agent; Remove TiO
2Outside the whisker, can also be ZnO, SiC whisker.
The present invention carries out surface treatment by adding dispersion agent to nanoparticle and whisker, strengthen particle or the dispersiveness of whisker in dispersion medium, and the strong shearing action by the high speed homogenization dispersion machine is opened the soft-agglomerated of nanoparticle, make nanoparticle better in dispersion medium, disperse, successfully coat polyaniline by the chemical oxidation situ aggregation method at nanoparticle or whisker surface, improve the absorbing property of nanoparticle or whisker.
Concrete preparation method is at TiO with the chemical oxidation situ aggregation method
2Nanoparticle or TiO
2The whisker surface coats polyaniline, and concrete preparation process is by weight, aniline hydrochloric acid to be joined by TiO
2Nanoparticle or TiO
2In the solution that whisker and dispersion agent and dispersion medium are formed, electronic stirring 0.5～1 hour, then under 15～25 ℃ normal temperature, the dispersion medium solution of dropping oxidizing agent continues to stir 3～4 hours again, and is last, suction filtration, with dehydrated alcohol and dilute hydrochloric acid washing, remove impurity and, promptly prepare polyaniline coating TiO repeatedly 60 ℃ of following vacuum-dryings 24 hours
2Nanoparticle or polyaniline coat TiO
2Whisker.
The raw material that the present invention is used for chemical oxidising polymerisation generation polyaniline is the aniline salt acid crystal, rather than aniline monomer solution.
TiO of the present invention
2Nanoparticle or TiO
2Whisker will pass through certain surface treatment, this surface-treated method: add in proportion in the dilute hydrochloric acid at Sodium dodecylbenzene sulfonate or polyoxyethylene glycol, TiO is added in the back that stirs
2Nanoparticle or whisker; This mixing suspension is at first used high speed homogenization dispersion machine high-speed stirring 10min, and then puts into Ultrasonic Cleaners sonic oscillation 20min.
Polyaniline coats TiO
2Nanoparticle and whisker make TiO
2New absorption peak occurs in the UV-light zone, not only absorbed UV-light, can also well absorb visible light and near infrared light.
The invention has the advantages that surface treated nanoparticle or whisker can well be dispersed in the dispersion medium, realized compound on nanoscale of organism and inorganics, and polyaniline coats TiO
2Nanoparticle and Preparation of Whiskers technology are also simple and easy to do.
Four, description of drawings
No accompanying drawing
Five, embodiment
Below by embodiment the specific embodiment of the present invention is described:
Embodiment 1: dispersion agent Sodium dodecylbenzene sulfonate 0.4g is dissolved in the hydrochloric acid soln of 400ml 0.2mol/L, adds TiO then
2Nanoparticle 1g, and with about high speed dispersion clarifixator high-speed stirring 10min, at this moment dispersion system is creamy white; Continuation is carried out sonic oscillation 20min with ultrasonic cleaner; Add 1g aniline hydrochloric acid then, at this moment milky solution becomes ash a little; The hydrochloric acid soln (the 1.75g ammonium persulphate being dissolved in the solution of 50ml dilute hydrochloric acid) of Dropwise 5 0ml ammonium persulphate behind the continuation stirring 20min, the control dropping time is about 10min, at this moment solution colour begins to gradually become mazarine by shallow and dark; Continue to stir 3～4 hours, color is by dark blue-blue-black-bluish-green-green; Last suction filtration, and use 0.06mol/L hydrochloric acid soln repetitive scrubbing again 3,4 times with absolute ethanol washing up to the filtrate clarification repeatedly earlier; Product in vacuum drying oven 60 ℃ dry 24 hours down, promptly obtain polyaniline and coat TiO
2Nanoparticle.
Embodiment 2: with example 1, wherein dispersion agent is polyoxyethylene glycol 2g, promptly obtains polyaniline and coats TiO
2Nanoparticle
Embodiment 3: with example 1, wherein TiO
2Nanoparticle changes TiO into
2Whisker obtains polyaniline and coats TiO
2Whisker.
Embodiment 4: with example 1, wherein dispersion agent is polyoxyethylene glycol 2g, TiO
2Nanoparticle changes TiO into
2Whisker obtains polyaniline and coats TiO
2Whisker.
Claims (6)
1. polyaniline clad nano TiO
2And polyaniline coats TiO
2Whisker is characterized in that its feed composition and weight part are as follows:
TiO
2Nanoparticle or whisker 100
Aniline hydrochloric acid 0.1～200
Dispersion agent 0.1～50
Dispersion medium 1000～20000
The equivalence ratio of oxygenant and aniline hydrochloric acid is 1: 1
1. described dispersion agent is Sodium dodecylbenzene sulfonate or polyoxyethylene glycol;
2. described dispersion medium is the hydrochloric acid soln of 0.2～1.0mol/L;
3. described oxygenant is an ammonium persulphate.
2. polyaniline clad nano TiO as claimed in claim 1
2And polyaniline coats TiO
2Whisker, the median size that it is characterized in that nanoparticle are at 10～100nm, and the diameter of whisker is 10～400nm, long 1～100 μ m.
3. polyaniline clad nano TiO as claimed in claim 1
2And polyaniline coats TiO
2Whisker is characterized in that employed nanoparticle is not only TiO
2, can also be ZnO, Co
3O
4, NiO, MoO
2, WO
3, SiC, Mn-Zn ferrite and carbon nanotube etc. inhale the wavefront modifier agent; Employed whisker is not only TiO
2, can also be ZnO, SiC whisker.
4. polyaniline clad nano TiO as claimed in claim 1
2And polyaniline coats TiO
2Whisker is characterized in that TiO
2Nanoparticle and whisker will be handled through certain surface: add certain amount of dispersant at certain dispersion medium, the back that stirs adds a certain amount of TiO
2High speed homogenization disperses to continue ultra-sonic dispersion 20min behind the 10min.
5. polyaniline clad nano TiO
2And polyaniline coats TiO
2The Preparation of Whiskers method, it is characterized in that it being with chemical oxidation situ aggregation method synthetic, promptly follow these steps to carry out: by weight, aniline hydrochloric acid is joined in the solution of nanoparticle or whisker and dispersion agent and dispersion medium composition, electronic stirring 0.5～1 hour, then under 15～25 ℃ normal temperature, the dispersion medium solution of dropping oxidizing agent again, continue to stir 3～4 hours, at last, suction filtration is repeatedly with dehydrated alcohol and dilute hydrochloric acid washing, remove impurity and, promptly prepare polyaniline coating TiO 60 ℃ of following vacuum-dryings 24 hours
2Nanoparticle or whisker.
6. polyaniline as claimed in claim 5 coats TiO
2Nanoparticle and Preparation of Whiskers method, it is characterized in that being used for the raw material that chemical oxidising polymerisation generates polyaniline is the aniline salt acid crystal, rather than aniline monomer solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100379653A CN1821315A (en) | 2006-01-24 | 2006-01-24 | Polyaniline coated nano TiO2 and poly aniline coated TiO2 whisker and their preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100379653A CN1821315A (en) | 2006-01-24 | 2006-01-24 | Polyaniline coated nano TiO2 and poly aniline coated TiO2 whisker and their preparing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1821315A true CN1821315A (en) | 2006-08-23 |
Family
ID=36922896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006100379653A Pending CN1821315A (en) | 2006-01-24 | 2006-01-24 | Polyaniline coated nano TiO2 and poly aniline coated TiO2 whisker and their preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1821315A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298698B (en) * | 2008-01-24 | 2010-04-21 | 西南交通大学 | Method for surface in situ synthesis of conductive polyaniline PANi by using four acicular type zinc oxide crystal whisker T-ZnOw |
| CN101525488B (en) * | 2009-04-03 | 2011-01-05 | 昆明理工大学 | Tungsten carbide/conductive polyaniline composite particle and preparation method thereof |
| CN102783500A (en) * | 2012-08-21 | 2012-11-21 | 昆明理工大学 | Nano polyaniline/ZnO composite antibacterial agent and preparation method thereof |
| CN101270236B (en) * | 2008-05-19 | 2013-04-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Nano-polyaniline-silicon dioxide-titanium dioxide electricity conductive pigment and preparation method thereof |
| CN103861571A (en) * | 2014-03-06 | 2014-06-18 | 西安交通大学 | Preparation method, application and regeneration method of polyaniline and titanium dioxide composite adsorbent |
| CN105036072A (en) * | 2015-05-22 | 2015-11-11 | 武汉理工大学 | Method for improving conductivity of modified titanium dioxide nanotube |
| CN105219217A (en) * | 2015-10-08 | 2016-01-06 | 中国石油天然气股份有限公司 | Non-dissolving out type low surface energy antifouling paint for oil field pipeline |
| CN106065126A (en) * | 2016-08-19 | 2016-11-02 | 广州市丰驰新材料有限公司 | A kind of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch and preparation method thereof |
| CN110773238A (en) * | 2019-10-16 | 2020-02-11 | 华南理工大学 | Polyaniline-coated WO 2.72Nano-rod composite material and preparation method and application thereof |
| CN111040474A (en) * | 2019-12-03 | 2020-04-21 | 河南佰利联新材料有限公司 | Conductive titanium dioxide and preparation method thereof |
| CN114146732A (en) * | 2021-11-30 | 2022-03-08 | 中国矿业大学(北京) | Polyaniline modified TiO2Composite nanofiber membrane and preparation method and application thereof |
-
2006
- 2006-01-24 CN CNA2006100379653A patent/CN1821315A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298698B (en) * | 2008-01-24 | 2010-04-21 | 西南交通大学 | Method for surface in situ synthesis of conductive polyaniline PANi by using four acicular type zinc oxide crystal whisker T-ZnOw |
| CN101270236B (en) * | 2008-05-19 | 2013-04-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Nano-polyaniline-silicon dioxide-titanium dioxide electricity conductive pigment and preparation method thereof |
| CN101525488B (en) * | 2009-04-03 | 2011-01-05 | 昆明理工大学 | Tungsten carbide/conductive polyaniline composite particle and preparation method thereof |
| CN102783500A (en) * | 2012-08-21 | 2012-11-21 | 昆明理工大学 | Nano polyaniline/ZnO composite antibacterial agent and preparation method thereof |
| CN103861571B (en) * | 2014-03-06 | 2015-12-09 | 西安交通大学 | The preparation method of polyaniline composite titanium dioxide adsorbent, application and renovation process |
| CN103861571A (en) * | 2014-03-06 | 2014-06-18 | 西安交通大学 | Preparation method, application and regeneration method of polyaniline and titanium dioxide composite adsorbent |
| CN105036072A (en) * | 2015-05-22 | 2015-11-11 | 武汉理工大学 | Method for improving conductivity of modified titanium dioxide nanotube |
| CN105036072B (en) * | 2015-05-22 | 2017-03-22 | 武汉理工大学 | Method for improving conductivity of modified titanium dioxide nanotube |
| CN105219217A (en) * | 2015-10-08 | 2016-01-06 | 中国石油天然气股份有限公司 | Non-dissolving out type low surface energy antifouling paint for oil field pipeline |
| CN106065126A (en) * | 2016-08-19 | 2016-11-02 | 广州市丰驰新材料有限公司 | A kind of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch and preparation method thereof |
| CN110773238A (en) * | 2019-10-16 | 2020-02-11 | 华南理工大学 | Polyaniline-coated WO 2.72Nano-rod composite material and preparation method and application thereof |
| CN111040474A (en) * | 2019-12-03 | 2020-04-21 | 河南佰利联新材料有限公司 | Conductive titanium dioxide and preparation method thereof |
| CN111040474B (en) * | 2019-12-03 | 2022-03-18 | 河南佰利联新材料有限公司 | Conductive titanium dioxide and preparation method thereof |
| CN114146732A (en) * | 2021-11-30 | 2022-03-08 | 中国矿业大学(北京) | Polyaniline modified TiO2Composite nanofiber membrane and preparation method and application thereof |
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