CN103232781A - Preparation method of carbon-nanotube-reinforced polyaniline metal anticorrosive paint - Google Patents
Preparation method of carbon-nanotube-reinforced polyaniline metal anticorrosive paint Download PDFInfo
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- CN103232781A CN103232781A CN2013101590887A CN201310159088A CN103232781A CN 103232781 A CN103232781 A CN 103232781A CN 2013101590887 A CN2013101590887 A CN 2013101590887A CN 201310159088 A CN201310159088 A CN 201310159088A CN 103232781 A CN103232781 A CN 103232781A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 66
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000003973 paint Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 56
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 56
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 31
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 31
- 239000007790 solid phase Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 56
- 239000006185 dispersion Substances 0.000 claims description 29
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 28
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000004220 aggregation Methods 0.000 claims description 7
- 230000002776 aggregation Effects 0.000 claims description 7
- 230000001186 cumulative effect Effects 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 239000013535 sea water Substances 0.000 abstract 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 13
- 229920001940 conductive polymer Polymers 0.000 description 12
- 239000002322 conducting polymer Substances 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 238000005536 corrosion prevention Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101000608154 Homo sapiens Peroxiredoxin-like 2A Proteins 0.000 description 1
- 102100039896 Peroxiredoxin-like 2A Human genes 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- OIRDTQYFTABQOQ-UHTZMRCNSA-N Vidarabine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@@H]1O OIRDTQYFTABQOQ-UHTZMRCNSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 210000000617 arm Anatomy 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention provides a preparation method of a carbon-nanotube-reinforced polyaniline metal anticorrosive paint, which comprises the following steps: carrying out ultrasonic treatment on carbon nanotubes (which account for 1-25 wt% of the solid phase) and polyaniline (which account for 20-60 wt% of the solid phase) for 30-45 minutes to be dispersed in an organic solvent, thereby forming a disperse system I; dissolving polymethyl methacrylate (PMMA) (which account for 30-70 wt% of the solid phase) in an organic solvent to obtain a disperse system II; thoroughly mixing the disperse system I and disperse system II under the conditions of ultrasonic and stirring; and volatilizing the organic solvent at 40-50 DEG C to obtain a viscous mixture with higher viscosity, which is the metal anticorrosive paint. The composite anticorrosive paint composed of the PMMA, polyaniline and carbon nanotubes has the advantages of simple preparation technique, convenient later coating technique and favorable anticorrosive effect, and is suitable to be used as a metal anticorrosive paint for a seawater environment. The invention solves the problem of high preparation cost and complex coating technique of the existing steel anticorrosive paint in a seawater environment, and enhances the anticorrosive effect.
Description
Technical field
The present invention relates to a kind of preparation method of conducting polymer protective system, especially a kind of carbon nanotube strengthens the preparation method of the metal anti-corrosive paint of polyaniline.
Background technology
Corrosion of metal is ubiquitous, is the main factor that causes multiclass facility, equipment Ordinary Wear and Tear, and particularly for the equipment that uses in briny environment for a long time, corrosion can be faster.Have statistics to show that hardware and the material scrapped because of corrosion account for 1/3 of metal ultimate production, financial loss is huge unusually.Developing rapidly of conduction high polymer brought new favourable turn for the solution of this problem.At first DeBerry finds, can make the stainless steel surface active passivation and have corrosion stability with the synthetic polyaniline film of electrochemical process in acidic medium, and these characteristics have caused people's attention.It is found that in most metallic surfaces to be the matrix material of main component by electrochemistry or coated with conducting polymer composite afterwards, can play the rot-resistant effect at certain Cheng Du.From then on people have begun the applied research of conducting polymer film in the corrosion prevention field.
Polyaniline has unique chemical, electrochemistry, optical property as a kind of new functional macromolecule material, in fields such as the energy, electromagnetic shielding, anticorrosion and electrochromism wide application prospect is arranged.Proved that polyaniline can form one deck passive film at steel surface, can increase substantially the antiseptic power of metal salt tolerance, and polyaniline paint has unique scratch resistance and corrosion resistance, is a kind of novel metal corrosion prevention coating that is particularly suitable for being applied under the rigor condition such as ocean and space flight.
Polyaniline is with its good chemical stability and electrochemical reversibility, and good anti-corrosion of metal characteristic becomes one of the fastest functional materials of present progress.Be base mateiral with the polyaniline, developing many novel materials at present, but no matter be all to be powder by chemical oxidation or the polyaniline of electrochemical oxidation gained, be difficult to the processing that is shaped, and its electric conductivity is mutually more far short of what is expected than also with metal.These shortcomings of conducting polymer composite have directly influenced its mass-producing and have used.Both ways conducting polymer composite various trials have been done around above problem people.At first be through the row chemical graft to conducting polymer, make prepared conducting polymer not only keep high molecular electroconductibility, and has a solubility, be conducive to processing, but the raising that experimental results show that all solubilities is cost to sacrifice electroconductibility all, the electric conductivity of the conducting polymer composite of feasible preparation all descends to some extent, has changed the conductivity of conducting polymer composite.In addition, to put forward to develop the water colloidal dispersion system be to solve the important method that is difficult to the forming process shortcoming for Vincent and Armes etc.At present, people have developed polyaniline coating inorganic nanoparticles (SiO for example
2, TiO
2, WC etc.) etc. material, polyaniline coats organic nanometer granule materials such as (for example PS, APS etc.).These materials that have polyaniline to coat can solve the processibility of polyaniline to a certain extent.Zhi Bei conducting polymer composite has had the common property of conducting polymer and inorganic materials like this, and still, the electric conductivity of prepared matrix material is lower, and the shaped material of processing gained is still based on coating or film.
With regard to the preparation protective system, can become dispersion system in order to apply with preparation of metal oxides polyaniline or polyaniline; Also can produce water miscible polyaniline, the coating that is applied with the form of its aqueous solution; Can also be that polyaniline is dispersed in the other flexible high polymer and forms composite coating.But it is that the coating electric conductivity is not high that the corrosion protection coating of preparation like this has the shortcoming of a maximum, influences its preservative effect.
Summary of the invention
The object of the invention is to prepare polyaniline and the PAMM blend protective system that a kind of carbon nanotube is wild phase, and the conductive polymer polyanilinc protective system that adopts method of the present invention to prepare has physical properties and stablizes, is easy to characteristics such as shaping is processed, preservative effect is good.
The present invention realizes by following technical proposal: a kind of carbon nanotube strengthens the preparation method of the metal anti-corrosive paint of polyaniline, following each step of process:
(1) carbon nanotube that will account for solid phase quality 1～25% with account for solid mutually the polyaniline of quality 20～60% be dispersed in the organic solvent through ultrasonic 30～45min, form the dispersion system I, wherein volume of organic solvent is 3:1 with the ratio of carbon nanotube and polyaniline cumulative volume;
(2) polymethylmethacrylate (PMMA) that will account for solid phase quality 30～70% adds in the organic solvent and is dissolved into the dispersion system II, and wherein the mass ratio of the quality of organic solvent and polymethylmethacrylate is 10:1;
(3) with step (1) dispersions obtained be I and step (2) dispersions obtained be II ultrasonic and stir under fully mix, and at 40～50 ℃ of volatilization organic solvents down, obtain the higher viscous state mixture of viscosity, be metal anti-corrosive paint.
The solid phase quality of described step (1) or (2) is the total mass of polyaniline, polymethylmethacrylate and carbon nanotube.
The carbon nanotube of described step (1) activates 3～5 hours through mixing acid at 50 ℃～60 ℃ earlier.
Described mixing acid is the mixing acid that the vitriol oil and concentrated nitric acid mix for 3:1 by volume.
The carbon nanotube of described step (1) and polyaniline are coated on carbon nano tube surface by situ aggregation method with polyaniline earlier before adding.
The organic solvent of described step (1) and step (2) is tetrahydrofuran (THF) or chloroform.
It is wild phase with the preparation polyaniline is that the matrix material of main raw reaches and strengthens briny environment rot-resistant purpose that the present invention adopts carbon nanotube.The composite anticorrosion coating preparation technology who is made up of PMMA, polyaniline, carbon nanotube of the present invention's preparation is simple, the later stage coating processes is convenient, favorable anti-corrosion effect, and suitable metal anti-corrosive paint as briny environment uses.Solve steel anti-corrosive coating preparation cost height, coating processes complicated problems in the existing briny environment, and improved preservative effect.
Embodiment
The present invention will be further described below by embodiment.
Embodiment 1
(1) carbon nanotube activates 5 hours for the mixing acid that 3:1 mixes at 50 ℃ by volume through the vitriol oil and concentrated nitric acid earlier, the carbon nanotube 0.3g that will account for solid phase quality 12% again with account for solid mutually the polyaniline 1.2g of quality 48% be dispersed in through ultrasonic 30min and form the dispersion system I in the tetrahydrofuran (THF), wherein solid phase quality is polyaniline, the total mass of polymethylmethacrylate and carbon nanotube, the volume of tetrahydrofuran (THF) is 3:1 with the ratio of carbon nanotube and polyaniline cumulative volume, and carbon nanotube and polyaniline are coated on carbon nano tube surface by situ aggregation method with polyaniline earlier before adding;
(2) polymethylmethacrylate (PMMA) 1.0g that will account for solid phase quality 40% adds in the tetrahydrofuran (THF) and is dissolved into the dispersion system II, and wherein the mass ratio of the quality of tetrahydrofuran (THF) and polymethylmethacrylate is 10:1;
(3) with step (1) dispersions obtained be I and step (2) dispersions obtained be II ultrasonic and stir under fully mix, and at 45 ℃ of volatilization organic solvents down, obtain the higher viscous state mixture of viscosity, be metal anti-corrosive paint.
The gained protective system is applied to clean copper sheet surface, and thickness 0.5mm places the NaCl solution 60 days of 0.5mol/L, does not find that copper sheet has corrosion phenomenon.
Embodiment 2
(1) carbon nanotube activates 4 hours for the mixing acid that 3:1 mixes at 60 ℃ by volume through the vitriol oil and concentrated nitric acid earlier, the carbon nanotube that will account for solid phase quality 1% again with account for solid mutually the polyaniline of quality 60% be dispersed in through ultrasonic 35min and form the dispersion system I in the chloroform, wherein solid phase quality is the total mass of polyaniline, polymethylmethacrylate and carbon nanotube, the volume of chloroform is 3:1 with the ratio of carbon nanotube and polyaniline cumulative volume, and carbon nanotube and polyaniline are coated on carbon nano tube surface by situ aggregation method with polyaniline earlier before adding;
(2) polymethylmethacrylate (PMMA) that will account for solid phase quality 39% adds in the chloroform and is dissolved into the dispersion system II, and wherein the mass ratio of the quality of chloroform and polymethylmethacrylate is 10:1;
(3) with step (1) dispersions obtained be I and step (2) dispersions obtained be II ultrasonic and stir under fully mix, and at 50 ℃ of volatilization organic solvents down, obtain the higher viscous state mixture of viscosity, be metal anti-corrosive paint.
The gained protective system is applied to clean copper sheet surface, and thickness 0.5mm places the NaCl solution 30 days of 0.5mol/L, does not find that copper sheet has corrosion phenomenon.
Embodiment 3
(1) carbon nanotube activates 3 hours for the mixing acid that 3:1 mixes at 55 ℃ by volume through the vitriol oil and concentrated nitric acid earlier, the carbon nanotube that will account for solid phase quality 25% again with account for solid mutually the polyaniline of quality 20% be dispersed in through ultrasonic 45min and form the dispersion system I in the tetrahydrofuran (THF), wherein solid phase quality is the total mass of polyaniline, polymethylmethacrylate and carbon nanotube, the volume of tetrahydrofuran (THF) is 3:1 with the ratio of carbon nanotube and polyaniline cumulative volume, and carbon nanotube and polyaniline are coated on carbon nano tube surface by situ aggregation method with polyaniline earlier before adding;
(2) polymethylmethacrylate (PMMA) that will account for solid phase quality 55% adds in the tetrahydrofuran (THF) and is dissolved into the dispersion system II, and wherein the mass ratio of the quality of tetrahydrofuran (THF) and polymethylmethacrylate is 10:1;
(3) with step (1) dispersions obtained be I and step (2) dispersions obtained be II ultrasonic and stir under fully mix, and at 40 ℃ of volatilization organic solvents down, obtain the higher viscous state mixture of viscosity, be metal anti-corrosive paint.
The gained protective system is applied to clean copper sheet surface, and thickness 0.5mm places the NaCl solution 60 days of 0.5mol/L, does not find that copper sheet has corrosion phenomenon.
Embodiment 4
(1) carbon nanotube activates 5 hours for the mixing acid that 3:1 mixes at 60 ℃ by volume through the vitriol oil and concentrated nitric acid earlier, the carbon nanotube that will account for solid phase quality 10% again with account for solid mutually the polyaniline of quality 60% be dispersed in through ultrasonic 45min and form the dispersion system I in the chloroform, wherein solid phase quality is the total mass of polyaniline, polymethylmethacrylate and carbon nanotube, the volume of chloroform is 3:1 with the ratio of carbon nanotube and polyaniline cumulative volume, and carbon nanotube and polyaniline are coated on carbon nano tube surface by situ aggregation method with polyaniline earlier before adding;
(2) polymethylmethacrylate (PMMA) that will account for solid phase quality 30% adds in the chloroform and is dissolved into the dispersion system II, and wherein the mass ratio of the quality of chloroform and polymethylmethacrylate is 10:1;
(3) with step (1) dispersions obtained be I and step (2) dispersions obtained be II ultrasonic and stir under fully mix, and at 40～50 ℃ of volatilization organic solvents down, obtain the higher viscous state mixture of viscosity, be metal anti-corrosive paint.
The gained protective system is applied to clean copper sheet surface, and thickness 0.5mm places the NaCl solution 50 days of 0.5mol/L, does not find that copper sheet has corrosion phenomenon.
Embodiment 5
(1) carbon nanotube activates 5 hours for the mixing acid that 3:1 mixes at 50 ℃ by volume through the vitriol oil and concentrated nitric acid earlier, the carbon nanotube that will account for solid phase quality 10% again with account for solid mutually the polyaniline of quality 20% be dispersed in through ultrasonic 30min and form the dispersion system I in the tetrahydrofuran (THF), wherein solid phase quality is the total mass of polyaniline, polymethylmethacrylate and carbon nanotube, the volume of tetrahydrofuran (THF) is 3:1 with the ratio of carbon nanotube and polyaniline cumulative volume, and carbon nanotube and polyaniline are coated on carbon nano tube surface by situ aggregation method with polyaniline earlier before adding;
(2) polymethylmethacrylate (PMMA) that will account for solid phase quality 70% adds in the tetrahydrofuran (THF) and is dissolved into the dispersion system II, and wherein the mass ratio of the quality of tetrahydrofuran (THF) and polymethylmethacrylate is 10:1;
(3) with step (1) dispersions obtained be I and step (2) dispersions obtained be II ultrasonic and stir under fully mix, and at 50 ℃ of volatilization organic solvents down, obtain the higher viscous state mixture of viscosity, be metal anti-corrosive paint.
The gained protective system is applied to clean copper sheet surface, and thickness 0.5mm places the NaCl solution 60 days of 0.5mol/L, does not find that copper sheet has corrosion phenomenon.
Claims (6)
1. a carbon nanotube strengthens the preparation method of the metal anti-corrosive paint of polyaniline, it is characterized in that through following each step:
(1) carbon nanotube that will account for solid phase quality 1～25% with account for solid mutually the polyaniline of quality 20～60% be dispersed in the organic solvent through ultrasonic 30～45min, form the dispersion system I, wherein volume of organic solvent is 3:1 with the ratio of carbon nanotube and polyaniline cumulative volume;
(2) polymethylmethacrylate that will account for solid phase quality 30～70% adds in the organic solvent and is dissolved into the dispersion system II, and wherein the mass ratio of the quality of organic solvent and polymethylmethacrylate is 10:1;
(3) with step (1) dispersions obtained be I and step (2) dispersions obtained be II ultrasonic and stir under fully mix, and at 40～50 ℃ of volatilization organic solvents down, obtain the higher viscous state mixture of viscosity, be metal anti-corrosive paint.
2. carbon nanotube according to claim 1 strengthens the preparation method of the metal anti-corrosive paint of polyaniline, and it is characterized in that: the solid phase quality of described step (1) or (2) is the total mass of polyaniline, polymethylmethacrylate and carbon nanotube.
3. carbon nanotube according to claim 1 strengthens the preparation method of the metal anti-corrosive paint of polyaniline, it is characterized in that: the carbon nanotube of described step (1) activates 3～5 hours through mixing acid at 50 ℃～60 ℃ earlier.
4. carbon nanotube according to claim 1 strengthens the preparation method of the metal anti-corrosive paint of polyaniline, it is characterized in that: the carbon nanotube of described step (1) and polyaniline are coated on carbon nano tube surface by situ aggregation method with polyaniline earlier before adding.
5. carbon nanotube according to claim 1 strengthens the preparation method of the metal anti-corrosive paint of polyaniline, and it is characterized in that: the organic solvent of described step (1) and step (2) is tetrahydrofuran (THF) or chloroform.
6. carbon nanotube according to claim 3 strengthens the preparation method of the metal anti-corrosive paint of polyaniline, it is characterized in that: described mixing acid is the mixing acid that the vitriol oil and concentrated nitric acid mix for 3:1 by volume.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2013101590887A CN103232781A (en) | 2013-05-03 | 2013-05-03 | Preparation method of carbon-nanotube-reinforced polyaniline metal anticorrosive paint |
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| CN2013101590887A CN103232781A (en) | 2013-05-03 | 2013-05-03 | Preparation method of carbon-nanotube-reinforced polyaniline metal anticorrosive paint |
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Cited By (2)
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| CN104119760A (en) * | 2014-06-27 | 2014-10-29 | 苏州市盛百威包装设备有限公司 | Carbon nanotube coating for packing machine and preparation method thereof |
| CN107216803A (en) * | 2017-06-02 | 2017-09-29 | 李文 | A kind of anti-corrosion of metal composite coating and preparation method thereof |
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| CN101643608A (en) * | 2008-08-06 | 2010-02-10 | 中国科学院金属研究所 | Polyaniline modified metal carbon nanotube coating and preparation method thereof |
| CN102134410A (en) * | 2010-01-27 | 2011-07-27 | 曾永斌 | High-performance water-based anticorrosion paint and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119760A (en) * | 2014-06-27 | 2014-10-29 | 苏州市盛百威包装设备有限公司 | Carbon nanotube coating for packing machine and preparation method thereof |
| CN104119760B (en) * | 2014-06-27 | 2016-07-13 | 太原科技大学 | A kind of carbon nano-tube coating for packer and preparation method thereof |
| CN107216803A (en) * | 2017-06-02 | 2017-09-29 | 李文 | A kind of anti-corrosion of metal composite coating and preparation method thereof |
| CN107216803B (en) * | 2017-06-02 | 2019-07-26 | 李文 | A kind of anti-corrosion of metal composite coating and preparation method thereof |
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Application publication date: 20130807 |