CN106191967A - A kind of process of doped graphene in polypyrrole coating - Google Patents
A kind of process of doped graphene in polypyrrole coating Download PDFInfo
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- CN106191967A CN106191967A CN201610523826.5A CN201610523826A CN106191967A CN 106191967 A CN106191967 A CN 106191967A CN 201610523826 A CN201610523826 A CN 201610523826A CN 106191967 A CN106191967 A CN 106191967A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000000576 coating method Methods 0.000 title claims abstract description 46
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 31
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004070 electrodeposition Methods 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 11
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 11
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 11
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 4
- 238000000429 assembly Methods 0.000 claims description 4
- 230000000712 assembly Effects 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- -1 Sodium dialkyl sulfate Chemical class 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229940075397 calomel Drugs 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000006392 deoxygenation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to composite coating corrosion-resistant field, particularly to a kind of process of doped graphene in polypyrrole coating.The method is particularly as follows: prepare Graphene initially with liquid phase stripping method, subsequently this Graphene is added deionized water supersound process until being uniformly dispersed, obtain graphene suspension, then after a certain amount of pyrrole monomer being added together with surfactant under the conditions of lucifuge in this suspension and stirring and make it fully dissolve, it is passed through a period of time nitrogen to remove dissolved oxygen in solution and obtain synthetic solvent, finally by cyclic voltammetry metal surface electro-deposition polypyrrole/graphene composite coating after the pre-treatment under the conditions of lucifuge.This technical method technical process is simple, uniform and fine and close by the polypyrrole coating after doped graphene, it is possible to significantly improve the corrosion resisting property of metallic matrix.
Description
Technical field
The invention belongs to composite coating corrosion-resistant field, particularly to a kind of technique of doped graphene in polypyrrole coating
Method.
Background technology
Find that the polyaniline coating electrochemically synthesized in acid medium can make rustless steel from DeBerry in 1985
Surface passivation and since improve its barrier propterty, the corrosion resistance of electroconductive polymer coating is constantly subjected to people's with mechanism
Pay close attention to.Owing to conducting polymer materials has electric conductivity and corrosion resistance concurrently, therefore it has boundless in anticorrosive metal field
Application prospect.But polymer coating is in electrodeposition process, it is inevitably present some microdefects, have impact on coating
Compactness, during metal and alloy long service, corrosive medium can penetrate into matrix surface along these defects, right
Matrix causes corrosion failure, the most how to reduce porosity on the premise of not affecting polymer coating electrical conductivity and increases coating cause
Close property is the key technology that solution is presently required.
Graphene is the two dimensional crystal of only monoatomic thickness, and in Graphene, each carbon atom all uses sp2Hydridization, and tribute
Offering a remaining p orbital electron and form a big π key, pi-electron can move freely, and gives the electric conductivity that Graphene is excellent.
Summary of the invention
The present invention will have Graphene and the polypyrrole coating material of high-specific surface area, excellent mechanical performances and conductive capability
It is combined, it is thus achieved that conduction and the multifunctional composite of excellent corrosion-proof performance, before not reducing polymer coating electrical conductivity
Put the porosity reducing coating as far as possible, give full play to the advantage in terms of anti-corrosion and conduction of bi-material, avoid simultaneously
Chemical method prepares the complex process of polypyrrole composite coating, directly by electrochemical method in Graphene with pyrrole monomer solution
Synthesis PPy/ Graphene composite coating.
The preparation process of the present invention is:
(1) preparation of Graphene
Graphene uses liquid phase stripping method to prepare, and its technique is: prepared with dimethylformamide (DMF) by graphite powder
Become 0.2mg/mL suspension, after ultrasonic disperse 3～4h, take the supernatant and make centrifugal, dried, obtaining graphene powder；
(2) preparation of liquid is synthesized
The graphene powder obtained in step (1) is added in deionized water and supersound process 30～60min, disperseed
Uniform graphene suspension；Subsequently pyrrole monomer and sodium lauryl sulphate (SDS) are joined above-mentioned Graphene in suspension,
Again this suspension is placed in light resistant container carry out magnetic agitation process make pyrrole monomer be sufficiently uniformly dissolved, finally in this suspension
Liquid is passed through nitrogen and carries out deoxygenation process in case pyrrole monomer oxidation, and proceed supersound process and make Graphene at this suspension
In fully dispersed, obtain synthesize liquid,
In synthesis liquid, Graphene concentration is 5mg/mL～20mg/mL, and pyrrole monomer concentration is 20mg/mL～30mg/mL,
Sodium lauryl sulphate (SDS) concentration is 35mg/mL～55mg/mL,
In synthesis liquid process for preparation, the stirring of pyrrole monomer and course of dissolution all (are i.e. being kept away in the light tight container of black
Under optical condition) carry out, after being uniformly dissolved, pass first into nitrogen 10～20min and carry out deoxygenation process, be further continued for carrying out supersound process
10～20 minutes, it is ensured that Graphene is sufficiently mixed with pyrrole monomer and is uniformly dispersed；
(3) electro-deposition composite coating
Three electrode assemblies are used to carry out electro-deposition, wherein reference electrode by electrochemical cyclic voltammetry under the conditions of lucifuge
For saturated calomel electrode, auxiliary electrode is platinized platinum, and working electrode is metal rustless steel sample, and electrolyte is to obtain in step (2)
Synthesis liquid, electrodeposition temperature is 0～10 DEG C, and the Graphene after electro-deposition/polypyrrole composite coating deionized water cleans, dry
It is dry,
Working electrode is to carry out following process before metal rustless steel sample uses: be 10mm × 10mm rustless steel by surface area
Sheet material one end copper conductor of burn-oning is as contact conductor, and with the inactive face of epoxy encapsulation sample, and with No. 400-800
Sand papering, acetone are cleaned oil removing, are dried,
In electrochemical cyclic voltammetry, scanning potential region is-0.2～1.0VSCE, sweep speed is 30mV/s, circulation
10-20 time, it is thus achieved that coating layer thickness be 5-15um.
The beneficial effects of the present invention is: instant invention overcomes the polypyrrole coating compactness obtained in prior art
The shortcomings such as difference, porosity are big, by the intervention of Graphene, are filled with the defect of polypyrrole coating effectively.Additionally, due to height
Being combined of the Graphene of electric conductivity, the electric conductivity of polypyrrole coating have also been obtained and significantly improves.
Accompanying drawing explanation
Fig. 1 is the polymer coating sample surface morphology that embodiment 1 is obtained with embodiment 3；Wherein (a) is pyrrole monomer
The pure PPy coating that aqueous solution is obtained by electrochemical method, (b) is that Graphene/pyrroles's suspension is obtained by electrochemical method
PPy/ Graphene composite coating；
Can be seen that, compared to pure PPy coating, the compactness of PPy/ Graphene composite coating is significantly improved, this
It is owing to the intervention of Graphene can be effective as the filling of polypyrrole coating defect, thus the coating obtained more uniformly causes
Close.
Detailed description of the invention
Embodiment 1
2.5g pyrrole monomer and 4.3g sodium lauryl sulphate (SDS) are added in 100mL water, the stirring of pyrrole monomer and
Course of dissolution all in the light tight container of black (i.e. under the conditions of lucifuge) carry out, be passed through nitrogen 18min after being uniformly dissolved and carry out
Deoxygenation process, in case pyrrole monomer oxidation, obtains synthesizing liquid；
Using area be 10mm × 10mm rustless steel sheet material one end copper conductor of burn-oning as contact conductor, and seal with epoxy resin
The inactive face of dress sample, cleans oil removing, dried with 400-800 sand papering, acetone,
Controlling electrodeposition temperature by water-bath under the conditions of lucifuge is 5 DEG C, carries out electricity by electrochemical cyclic voltammetry heavy
Long-pending experiment, electrodeposition process uses three electrode assemblies: saturated calomel electrode makees auxiliary electrode, process as reference electrode, platinized platinum
The metal stainless steel substrates of above-mentioned process is as working electrode, and electrolyte is synthesis liquid obtained above, scanning potential region be-
0.2～1.0VSCE, sweep speed is 30mV/s, circulates 10 times, and the polypyrrole coating deionized water after electro-deposition cleans.
This example obtained polypyrrole coating surface uniformity poor (such as accompanying drawing 1 (a)), relative to matrix rustless steel, its
At acid (0.3mol/L H2SO4) corrosion potential improves 140mV in environment, corrosion rate drops to 0.4mm/a from 1.1mm/a.
Embodiment 2
1.0g Graphene is added in 100mL deionized water and supersound process 60min, obtain finely dispersed Graphene and hang
Supernatant liquid, joins above-mentioned Graphene in suspension by 2.5g pyrrole monomer and 4.3g sodium lauryl sulphate (SDS) subsequently, then should
Suspension is placed in light resistant container and carries out magnetic agitation and process and make pyrrole monomer be sufficiently uniformly dissolved, finally logical in this suspension
Enter nitrogen 18min carry out deoxygenation process in case pyrrole monomer oxidation, and proceed supersound process 20min make Graphene this hang
In supernatant liquid fully dispersed, obtain synthesize liquid；
The pretreatment of working electrode metal stainless steel substrates and electro-deposition prepare the technique of composite coating all with embodiment 1.
Compared with Example 1, its surface uniformity obtains the polypyrrole/graphene composite coating that the present embodiment is obtained
Significantly improving (such as accompanying drawing 1 (b)), relative to matrix rustless steel, it is at acid (0.3mol/L H2SO4) corrosion potential carries in environment
High 210mV, corrosion rate drops to 0.2mm/a from 1.1mm/a.
Embodiment 3
2.0g Graphene is added in 100mL deionized water and supersound process 60min, obtain finely dispersed Graphene and hang
Supernatant liquid, joins above-mentioned Graphene in suspension by 2.5g pyrrole monomer and 4.3g sodium lauryl sulphate (SDS) subsequently, then should
Suspension is placed in light resistant container and carries out magnetic agitation and process and make pyrrole monomer be sufficiently uniformly dissolved, finally logical in this suspension
Enter nitrogen 18min carry out deoxygenation process in case pyrrole monomer oxidation, and proceed supersound process 20min make Graphene this hang
In supernatant liquid fully dispersed, obtain synthesize liquid；
The pretreating process of working electrode metal stainless steel substrates is with embodiment 1.
Controlling electrodeposition temperature by water-bath under the conditions of lucifuge is 5 DEG C, carries out electricity by electrochemical cyclic voltammetry heavy
Long-pending experiment, electrodeposition process uses three electrode assemblies: saturated calomel electrode makees auxiliary electrode, process as reference electrode, platinized platinum
The metal stainless steel substrates of above-mentioned process is as working electrode, and electrolyte is synthesis liquid obtained above, scanning potential region be-
0.2～1.0VSCE, sweep speed is 30mV/s, circulates 15 times, and the polypyrrole coating deionized water after electro-deposition cleans.
The uniformity of the polypyrrole/graphene composite coating that the present embodiment is obtained is preferable with compactness, relative to matrix
Rustless steel, it is at acid (0.3mol/L H2SO4) corrosion potential improves 273mV in environment, corrosion rate drops to from 1.1mm/a
0.11mm/a。
Claims (7)
1. the process of a doped graphene in polypyrrole coating, it is characterised in that: the step of described method is,
(1) preparation of Graphene；
(2) preparation of liquid is synthesized；
(3) electro-deposition composite coating.
2. the process of doped graphene in polypyrrole coating as claimed in claim 1, it is characterised in that: step (1)
In, Graphene uses liquid phase stripping method to prepare, and its technique is, is configured to dimethylformamide (DMF) by graphite powder
0.2mg/mL suspension, takes the supernatant after ultrasonic disperse 3～4h and makees centrifugal, dried, obtaining graphene powder.
3. the process of doped graphene in polypyrrole coating as claimed in claim 1, it is characterised in that: step (2)
In, the Graphene obtained in step (1) is added in deionized water and supersound process 30～60min, obtain finely dispersed stone
Ink alkene suspension；Subsequently pyrrole monomer and sodium lauryl sulphate are joined above-mentioned Graphene in suspension, then by this suspension
It is placed in light resistant container and carries out magnetic agitation, this suspension the most backward is passed through nitrogen, and proceeds supersound process, closed
Become liquid.
4. the process of doped graphene in polypyrrole coating as claimed in claim 3, it is characterised in that: step (2)
In described synthesis liquid, Graphene concentration is 5mg/mL～20mg/mL, and pyrrole monomer concentration is 20mg/mL～30mg/mL, ten
Sodium dialkyl sulfate concentration is 35mg/mL～55mg/mL.
5. the process of doped graphene in polypyrrole coating as claimed in claim 3, it is characterised in that: step (2)
In, being passed through the nitrogen time is 10～20min, and the time proceeding supersound process after being passed through nitrogen is 10～20min.
6. the process of doped graphene in polypyrrole coating as claimed in claim 1, it is characterised in that: step (3)
In, use three electrode assemblies to carry out electro-deposition by electrochemical cyclic voltammetry under the conditions of lucifuge, wherein reference electrode is full
And calomel electrode, auxiliary electrode is platinized platinum, and working electrode is metal rustless steel sample, and electrolyte is the conjunction obtained in step (2)
Becoming liquid, electrodeposition temperature is 0～10 DEG C, and the Graphene after electro-deposition/polypyrrole composite coating deionized water cleans, is dried.
7. the process of doped graphene in polypyrrole coating as claimed in claim 6, it is characterised in that: step (3)
In, in electrochemical cyclic voltammetry, scanning potential region is-0.2～1.0VSCE, sweep speed is 30mV/s, circulates 10-20
Secondary.
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Cited By (6)
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| CN107254705A (en) * | 2017-06-09 | 2017-10-17 | 常州大学 | A kind of preparation technology of nano TiN PANI composite conductive polymer coatings |
| CN109786124A (en) * | 2018-12-05 | 2019-05-21 | 南通科技职业学院 | A kind of flexible asymmetric super-capacitor and preparation method thereof |
| CN111128472A (en) * | 2019-12-17 | 2020-05-08 | 浙江大学 | Method for preparing conductive polymer film on graphene surface through electrodeposition |
| CN111593347A (en) * | 2020-06-02 | 2020-08-28 | 太原理工大学 | Flexible composite film material and preparation method thereof |
| CN113789554A (en) * | 2021-08-16 | 2021-12-14 | 华中科技大学 | Magnesium alloy with protective coating and preparation method and application thereof |
| CN114307674A (en) * | 2021-12-28 | 2022-04-12 | 北京林业大学 | Preparation method of special hydrophilic and hydrophobic membrane based on electric gradient morphology regulation |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107254705A (en) * | 2017-06-09 | 2017-10-17 | 常州大学 | A kind of preparation technology of nano TiN PANI composite conductive polymer coatings |
| CN107254705B (en) * | 2017-06-09 | 2020-12-11 | 常州大学 | Preparation process of nano TiN-PANI composite conductive polymer coating |
| CN109786124A (en) * | 2018-12-05 | 2019-05-21 | 南通科技职业学院 | A kind of flexible asymmetric super-capacitor and preparation method thereof |
| CN109786124B (en) * | 2018-12-05 | 2024-04-05 | 南通南京大学材料工程技术研究院 | Flexible asymmetric supercapacitor and preparation method thereof |
| CN111128472A (en) * | 2019-12-17 | 2020-05-08 | 浙江大学 | Method for preparing conductive polymer film on graphene surface through electrodeposition |
| CN111593347A (en) * | 2020-06-02 | 2020-08-28 | 太原理工大学 | Flexible composite film material and preparation method thereof |
| CN113789554A (en) * | 2021-08-16 | 2021-12-14 | 华中科技大学 | Magnesium alloy with protective coating and preparation method and application thereof |
| CN113789554B (en) * | 2021-08-16 | 2022-12-02 | 华中科技大学 | Magnesium alloy with protective coating and preparation method and application thereof |
| CN114307674A (en) * | 2021-12-28 | 2022-04-12 | 北京林业大学 | Preparation method of special hydrophilic and hydrophobic membrane based on electric gradient morphology regulation |
| CN114307674B (en) * | 2021-12-28 | 2022-12-09 | 北京林业大学 | Preparation method of special hydrophilic and hydrophobic membrane based on electric gradient morphology regulation |
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Application publication date: 20161207 Assignee: Senbiao Technology Services (Shandong) Co.,Ltd. Assignor: CHANGZHOU University Contract record no.: X2023980051006 Denomination of invention: A Process Method for Doping Graphene into Polypyrrole Coatings Granted publication date: 20190125 License type: Common License Record date: 20231209 |
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