CN104593847A - Preparation method of metal surface graphene/polypyrrole protective composite film - Google Patents
Preparation method of metal surface graphene/polypyrrole protective composite film Download PDFInfo
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- CN104593847A CN104593847A CN201510019390.1A CN201510019390A CN104593847A CN 104593847 A CN104593847 A CN 104593847A CN 201510019390 A CN201510019390 A CN 201510019390A CN 104593847 A CN104593847 A CN 104593847A
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Abstract
The invention belongs to the technical field of metal protection, and relates to a preparation method of a graphene/polypyrrole protective composite film and application of the graphene/polypyrrole protective composite film on different metal surfaces. The preparation method comprises the steps of preoxidation, oxidation, compounding, electrodeposition and electroreduction. The electrodeposition is adopted to deposit the graphene oxide and polypyrrole on the metal surface to form a composite film, and the electrochemical reduction is performed to obtain the high-corrosion-resistance conductive polymer film. The method comprehensively utilizes the advantages of the graphene and conductive polymer, and overcomes the defects of low solubility and difficulty in processing of the conductive polymer. The method has the advantages of novel design, scientific principle, simple process, simple operation, high preparation efficiency, favorable corrosion resistance, no pollution and no waste.
Description
Technical field:
The invention belongs to metal protection technical field, relate to the anti-film of a kind of compound for metallic surface, particularly a kind of Graphene/polypyrrole protection preparation method of laminated film and the security application to different metal surface.
Background technology:
In practice, serious corrosion wasting phenomenon is there is in metal in the application process in the fields such as railway, mine, bridge construction, shipping industry, according to incompletely statistics, the direct economic loss that the annual because metallic corrosion of China causes is up to nearly hundred billion yuans, therefore solve metallic corrosion problem preferably, great economic benefit and social benefit will be brought.At present, following method is roughly comprised to the rotproofing of metallic surface: the first, in metallic surface the organic and mineral compound of coating such as paint, plastics, rubber, pitch etc., the second, at protective layer such as metallic surface plating inert metal or alloy etc., 3rd, adopt chemistry or electrochemical method to make metallic surface form stable compound rete, 4th, " Dacroment " technological synthesis is adopted to utilize all kinds of protective layers etc., although aforesaid method can reach certain preservative effect, but because the cost of the methods such as Nitrizing Treatment and organosilane surface treatment is higher, bonderizing easily causes again heavy-metal pollution to bring numerous negative issue, by the matrix material of laminated structure such as sheet mica, the effect be doped in the inorganic materials protective system of the scale structures such as aluminium powder in protective system is not only not satisfactory, and chromic salt has stronger toxicity and easily causes negative issue (as Chinese patent 201210066163.0).
In recent years, Graphene becomes hot research topic gradually, because Graphene has good barrier property to air and glassware for drinking water, good transfer barrier can be formed in metallic surface, reach air, physical barrier between water and metal, realize good preservative effect, thus get more and more people's extensive concerning.Research shows, conductive polymers is used for corrosion protective coating, good preservative effect can be reached, because conductive polymers inducing metal surface passivation can form the good preservative coat of one deck, but due to the solubleness of conductive polymers and plasticity-poor, so seriously limit the application of conductive polymers on metal protection.In prior art, people (the YanHua Lei such as YanHua Lei, Nan Sheng et al.Corrosion Science:Electrochemicalsynthesis of polypyrrole films on copper from physic solution forcorrosion protection, 2013, 76:302-309) adopt the method for electrochemical deposition at copper surface deposition one deck film of poly pyrrole, by studying its corrosion behavior in NaCl solution, indicate film of poly pyrrole and can significantly improve corrosive nature to metallic copper, but along with the prolongation of time, the oxidizing property of film of poly pyrrole is lost gradually and is caused antiseptic property to decrease.Therefore, the present invention works out a kind of preparation method being prepared Graphene/polypyrrole protection laminated film by galvanic deposit and electrochemical reduction, is deposited and forms conducting polymer thin film on the metal surface, to realize good antiseptic property.
Summary of the invention:
Goal of the invention of the present invention is the shortcoming overcoming prior art existence, seek the preparation method designing a kind of Graphene/polypyrrole protection laminated film, be used for extending duration of service of polypyrrole by the physical barrier of Graphene, thus improve the antiseptic property of laminated film.
To achieve these goals, the preparation method of the metallic surface Graphene/polypyrrole protection laminated film related to of the present invention specifically comprises following processing step:
(1) preoxidation process: after the vitriol oil of 2g natural graphite, 1g Vanadium Pentoxide in FLAKES, 10ml massfraction 98% and 1g Potassium Persulphate mixing and stirring, preoxidation 0.5-18h under temperature control 80-90 DEG C condition, naturally cool to room temperature (20-25 DEG C) again and place 6-8h, then add that distilled water carries out diluting, suction filtration be washed to neutrality, obtain preoxidation graphite after drying stand-by;
(2) oxidising process: after preoxidation graphite and 46ml vitriol oil mixing and stirring, adopt ice bath device to control reaction system under 10-20 DEG C of condition, slowly add 6g potassium permanganate powder and constantly stir, then reaction system is placed in the oil bath stirring reaction 2-2.5h of 35-38 DEG C, continue reaction 15-20min after adding 100ml distilled water diluting again, finally add 300ml distilled water termination reaction; Add again 5-8ml weight percent concentration be 30% aqueous hydrogen peroxide solution to mixed solution presents golden yellow, carry out suction filtration, then to rinse with the aqueous hydrochloric acid of the massfraction 5% of 10 times of weight, obtain stable graphene oxide aqueous dispersion liquid for subsequent use;
(3) recombination process: above-mentioned graphene oxide aqueous dispersion liquid adding distil water is diluted to concentration 1mg/ml, then get 10ml graphene oxide aqueous dispersion liquid and add 10mg pyrroles wherein, the weight ratio of graphene oxide and pyrroles is made to be 1:1, stable graphene oxide chromium solution is obtained again through ultrasonic disperse, then pass into nitrogen 30-40min to remove the oxygen in graphene oxide chromium solution, prevent pyrroles from autoxidation polymerization occurring because of oxygen;
(4) electrodeposition process: by tinsel, saturated silver chloride electrode and platinum electrode are placed in graphene oxide chromium solution, wherein tinsel is worked electrode, saturated silver chloride electrode does reference electrode, platinum electrode does supporting electrode, commercially available electrochemical workstation (Shanghai occasion China CHI760D type) is utilized to determine to execute alive size and time length according to the dissimilar of tinsel, tinsel deposited on silicon is made to form one deck graphene oxide/film of poly pyrrole, take out tinsel distilled water flushing 2-3 all over after to put into baking oven temperature control 60-70 DEG C of dry 3-4h for subsequent use,
(5) electro-reduction process: dried tinsel is put into the aqueous sodium persulfate solution that concentration is 50g/L, continue to pass into nitrogen 30-40min, volt-ampere cyclic curve method is taked to apply the cyclical voltage of-1.5-0V to tinsel, 10 circles are scanned under the scanning speed of 50mv/s, the graphene oxide in graphene oxide/film of poly pyrrole is made to be reduced into Graphene, then tinsel taking-up distilled water flushing is clean and put into baking oven temperature control 50-60 DEG C of drying 3 hours, realize preparing deposited oxide Graphene/polypyrrole protection laminated film on the surface at tinsel.
Graphene oxide and polypyrrole compared with prior art, by the method for galvanic deposit, are deposited on metallic surface and form one deck complex thin film by the present invention, then by the method for electrochemical reduction, obtain the conducting polymer thin film with good antiseptic property; Not only fully utilize the advantage of Graphene and conductive polymers in the method, also avoid conductive polymers indissoluble solution, unmanageable shortcoming preferably; The method is novel in design, scientific in principle, and process is simple, and operate simple and easy, preparation efficiency is high, and Corrosion Protection is good, and pollution-free, nothing waste.
Accompanying drawing illustrates:
Fig. 1 is preparation method's process flow diagram of the metallic surface Graphene/polypyrrole protection laminated film that the present invention relates to.
Fig. 2 is the structure sectional view after tinsel surface deposition Graphene in the present invention/polypyrrole protection laminated film, and wherein 1 is tinsel, and 2 is Graphene basic unit, and 3 is polypyrrole conductive polymers.
Fig. 3 is the preparation principle schematic diagram of Graphene in the present invention/polypyrrole protection laminated film.
Fig. 4 is the carbon steel coupon of deposited graphite alkene in embodiments of the invention 2/polypyrrole protection laminated film (being all called for short laminated film below) and does not deposit the Tafel polarization curve figure of carbon steel coupon of laminated film, wherein 1 is the Tafel polarization curve figure of the carbon steel coupon not depositing laminated film, and 2 is the Tafel polarization curve figure of the carbon steel coupon of deposition laminated film.
Fig. 5 is the copper sheet of deposited graphite alkene in embodiments of the invention 3/polypyrrole protection laminated film (being all called for short laminated film below) and does not deposit the Tafel polarization curve figure of copper sheet of laminated film, wherein 1 is the Tafel polarization curve figure of the copper sheet not depositing laminated film, and 2 is the Tafel polarization curve figure of the copper sheet of deposition laminated film.
Fig. 6 is the aluminium flake of deposited graphite alkene in embodiments of the invention 4/polypyrrole protection laminated film (being all called for short laminated film below) and does not deposit the Tafel polarization curve figure of aluminium flake of laminated film, wherein 1 is the Tafel polarization curve figure of the aluminium flake not depositing laminated film, and 2 is the Tafel polarization curve figure of the aluminium flake of deposition laminated film.
Embodiment:
The present invention is described in further detail by embodiment below in conjunction with accompanying drawing, but the present invention is not limited to following embodiment.
Embodiment 1:
The concrete steps of the preparation method of the metallic surface Graphene related in this enforcement/polypyrrole protection laminated film are:
(1) preoxidation process: after the vitriol oil of 2g natural graphite, 1g Vanadium Pentoxide in FLAKES, 10ml massfraction 98% and 1g Potassium Persulphate mixing and stirring, preoxidation 0.5-18h under temperature control 80-90 DEG C condition, naturally cool to room temperature (20-25 DEG C) again and place 6-8h, then add that distilled water carries out diluting, suction filtration be washed to neutrality, obtain preoxidation graphite after drying stand-by;
(2) oxidising process: after preoxidation graphite and 46ml vitriol oil mixing and stirring, adopt ice bath device to control reaction system under 10-20 DEG C of condition, slowly add 6g potassium permanganate powder and constantly stir, then reaction system is placed in the oil bath stirring reaction 2-2.5h of 35-38 DEG C, continue reaction 15-20min after adding 100ml distilled water diluting again, finally add a large amount of 300ml distilled water termination reaction; Add again 5-8ml weight percent concentration be 30% aqueous hydrogen peroxide solution to mixed solution presents golden yellow, carry out suction filtration, use the aqueous hydrochloric acid of 10 times of weight (massfraction is 5%) to rinse again, obtain stable graphene oxide aqueous dispersion liquid for subsequent use;
(3) recombination process: above-mentioned graphene oxide aqueous dispersion liquid adding distil water is diluted to concentration 1mg/ml, then get 10ml graphene oxide aqueous dispersion liquid and add 10mg pyrroles wherein, the weight ratio of graphene oxide and pyrroles is made to be 1:1, stable graphene oxide chromium solution is obtained again through ultrasonic disperse, then pass into nitrogen 30-40min to remove the oxygen in graphene oxide chromium solution, prevent pyrroles from autoxidation polymerization occurring because of oxygen;
(4) electrodeposition process: by tinsel, saturated silver chloride electrode and platinum electrode are placed in graphene oxide chromium solution, wherein tinsel is worked electrode, saturated silver chloride electrode does reference electrode, platinum electrode does supporting electrode, commercially available electrochemical workstation (Shanghai occasion China CHI760D type) is utilized to determine to execute alive size and time length according to the dissimilar of tinsel, tinsel deposited on silicon is made to form one deck graphene oxide/film of poly pyrrole, take out tinsel distilled water flushing 2-3 all over after to put into baking oven temperature control 50-60 DEG C of dry 3-4h for subsequent use,
(5) electro-reduction process: dried tinsel is put into the aqueous sodium persulfate solution that concentration is 50g/L, continue to pass into nitrogen 30-40min, volt-ampere cyclic curve method is taked to apply the cyclical voltage of-1.5-0V to tinsel, 10 circles are scanned under the scanning speed of 50mv/s, the graphene oxide in graphene oxide/film of poly pyrrole is made to be reduced into Graphene, then tinsel taking-up distilled water flushing is clean and put into baking oven temperature control 50-60 DEG C of drying 3 hours, realize at tinsel deposited on silicon graphene oxide/polypyrrole protection laminated film.
Shanghai occasion China CHI 760D type electrochemical workstation is utilized to carry out Tafel polarization curve test (anti corrosion test) to the tinsel depositing Graphene/polypyrrole protection laminated film (being all called for short laminated film below) in the present embodiment, the tinsel depositing laminated film being placed on massfraction is in the sodium chloride aqueous solution of 3.5%, under open circuit voltage, within the scope of-1V to 1V, carry out polarization test with the scanning speed of 10mV/s, the known erosion resistance depositing the tinsel of laminated film improves a lot after tested.
Embodiment 2:
Get 20mg graphene oxide (or measuring certain volume according to the concentration of the graphene oxide dispersion of having demarcated (quantitatively to about 1mg/ml)), with ultrasonic cleaning instrument ultrasonic 15 ~ 20 minutes, obtain uniform graphene oxide dispersion, measure 20mg pyrrole monomer, be added drop-wise in above-mentioned graphene oxide dispersion, make the weight ratio 1:1 of graphene oxide and pyrroles, obtain uniform graphene oxide pyrroles dispersion liquid (abbreviation dispersion liquid) through magnetic agitation, nitrogen 30min is led to above-mentioned dispersion liquid, carbon steel thin slice, saturated silver chloride electrode and platinum electrode is put in dispersion liquid, utilize electrochemical workstation (Shanghai occasion China CHI 760D type) to apply voltage 0.8V and continue 5min, form Graphene/polypyrrole protection laminated film (being all called for short laminated film below) on carbon steel slice surfaces through galvanic deposit, then take out carbon steel thin slice distilled water flushing clean and through 50 DEG C of dry 3h, the sodium chloride aqueous solution that the carbon steel thin slice depositing laminated film and the carbon steel thin slice (as a comparison sample) that do not deposit laminated film put into massfraction 3.5% is respectively carried out electrochemical corrosion experimental, the Tafel polarization curve (as shown in Figure 4) of both tests under respective open circuit voltage, wherein curve 1 represents the polarization curve not having the carbon steel thin slice of galvanic deposit laminated film, curve 2 represents the polarization curve depositing the carbon steel thin slice of laminated film, known according to diagram, the corrosion potential of the carbon steel thin slice after galvanic deposit laminated film increases, corrosion current reduces, namely illustrate that galvanic deposit has the erosion resistance of the carbon steel thin slice of laminated film to improve a lot.
Embodiment 3:
Get 20mg graphene oxide (or measuring certain volume according to the concentration of the graphene oxide dispersion of having demarcated (quantitatively to about 1mg/ml)), with ultrasonic cleaning instrument ultrasonic 15 ~ 20 minutes, obtain uniform graphene oxide dispersion; Measure 20mg pyrrole monomer, be added drop-wise in above-mentioned graphene oxide dispersion, make the weight ratio 1:1 of graphene oxide and pyrroles, obtain uniform graphene oxide pyrroles dispersion liquid (abbreviation dispersion liquid) through magnetic agitation, nitrogen 30min is led to above-mentioned dispersion liquid; Copper foil, saturated silver chloride electrode and platinum electrode is put in dispersion liquid, electrochemical workstation (Shanghai occasion China CHI 760D type) is utilized to apply voltage 1.2V time length 1min, form Graphene/polypyrrole protection laminated film (being all called for short laminated film below) to copper foil on the surface through galvanic deposit, then take out copper foil distilled water flushing clean and through 50 DEG C of dry 3h; The copper foil depositing laminated film and the copper foil (as a comparison sample) that do not deposit laminated film are put into respectively massfraction be 3.5% sodium chloride aqueous solution carry out electrochemical corrosion experimental, the Tafel polarization curve (as shown in Figure 5) of both tests under respective open circuit voltage, wherein curve 1 represents the polarization curve not having the copper foil of galvanic deposit laminated film, curve 2 represents the polarization curve depositing the copper foil of laminated film, and the erosion resistance according to the copper foil after the known galvanic deposit laminated film of diagram improves a lot.
Embodiment 4:
Get 20mg graphene oxide (or measuring certain volume according to the concentration of the graphene oxide dispersion of having demarcated (quantitatively to about 1mg/ml)), with ultrasonic cleaning instrument ultrasonic 15 ~ 20 minutes, obtain uniform graphene oxide dispersion; Measure 20mg pyrrole monomer, be added drop-wise in above-mentioned graphene oxide dispersion, make the weight ratio 1:1 of graphene oxide and pyrroles, obtain uniform graphene oxide pyrroles dispersion liquid (abbreviation dispersion liquid) through magnetic agitation, nitrogen 30min is led to above-mentioned dispersion liquid; Aluminum slice, saturated silver chloride electrode and platinum electrode is put in dispersion liquid, electrochemical workstation (Shanghai occasion China CHI 760D type) is utilized to apply voltage 1.2V time length 3min, form Graphene/polypyrrole protection laminated film (being all called for short laminated film below) to aluminum slice on the surface through galvanic deposit, then take out aluminum slice distilled water flushing clean and through 60 DEG C of dry 3h; The aluminum slice depositing laminated film and the aluminum slice (as a comparison sample) that do not deposit laminated film are put into respectively massfraction be 3.5% sodium chloride aqueous solution carry out electrochemical corrosion experimental, the Tafel polarization curve (as shown in Figure 6) of both tests under respective open circuit voltage, wherein curve 1 represents the polarization curve not having the aluminum slice of galvanic deposit laminated film, curve 2 represents the polarization curve depositing the aluminum slice of laminated film, and the erosion resistance according to the aluminum slice after the known galvanic deposit laminated film of diagram improves a lot.
The corrosion potential of the carbon steel coupon in Comprehensive Correlation embodiment 2-4 before and after laminated film deposition, copper sheet, aluminium flake, concrete comparing result is as shown in the table:
Claims (2)
1. a preparation method for metallic surface Graphene/polypyrrole protection laminated film, is characterized in that specifically comprising following processing step:
(1) preoxidation process: after the vitriol oil of 2g natural graphite, 1g Vanadium Pentoxide in FLAKES, 10ml massfraction 98% and 1g Potassium Persulphate mixing and stirring, preoxidation 0.5-18h under temperature control 80-90 DEG C condition, naturally cool to 20-25 DEG C again and place 6-8h, then add that distilled water carries out diluting, suction filtration be washed to neutrality, obtain preoxidation graphite after drying stand-by;
(2) oxidising process: after preoxidation graphite and 46ml vitriol oil mixing and stirring, adopt ice bath device to control reaction system under 10-20 DEG C of condition, slowly add 6g potassium permanganate powder and constantly stir, then reaction system is placed in the oil bath stirring reaction 2-2.5h of 35-38 DEG C, continue reaction 15-20min after adding 100ml distilled water diluting again, finally add a large amount of 300ml distilled water termination reaction; Add again 5-8ml weight percent concentration be 30% aqueous hydrogen peroxide solution to mixed solution presents golden yellow, carry out suction filtration, then to rinse with the aqueous hydrochloric acid of the massfraction 5% of 10 times of weight, obtain stable graphene oxide aqueous dispersion liquid for subsequent use;
(3) recombination process: above-mentioned graphene oxide aqueous dispersion liquid adding distil water is diluted to concentration 1mg/ml, then get 10ml graphene oxide aqueous dispersion liquid and add 10mg pyrroles wherein, the weight ratio of graphene oxide and pyrroles is made to be 1:1, stable graphene oxide chromium solution is obtained again through ultrasonic disperse, then pass into nitrogen 30-40min to remove the oxygen in graphene oxide chromium solution, prevent pyrroles from autoxidation polymerization occurring because of oxygen;
(4) electrodeposition process: tinsel, saturated silver chloride electrode and platinum electrode are placed in graphene oxide chromium solution, wherein tinsel is worked electrode, saturated silver chloride electrode does reference electrode, platinum electrode does supporting electrode, commercially available electrochemical workstation is utilized to determine to execute alive size and time length according to the dissimilar of tinsel, make tinsel deposited on silicon form one deck graphene oxide/film of poly pyrrole, take out tinsel distilled water flushing 2-3 all over after to put into baking oven temperature control 50-60 DEG C of dry 3-4h for subsequent use;
(5) electro-reduction process: dried tinsel is put into the aqueous sodium persulfate solution that concentration is 50g/L, continue to pass into nitrogen 30-40min, volt-ampere cyclic curve method is taked to apply the cyclical voltage of-1.5-0V to tinsel, 10 circles are scanned under the scanning speed of 50mv/s, the graphene oxide in graphene oxide/film of poly pyrrole is made to be reduced into Graphene, then tinsel taking-up distilled water flushing is clean and put into baking oven temperature control 50-60 DEG C of drying 3 hours, realize at tinsel deposited on silicon graphene oxide/polypyrrole protection laminated film.
2. the preparation method of metallic surface according to claim 1 Graphene/polypyrrole protection laminated film, is characterized in that prepared Graphene/polypyrrole protection laminated film to be deposited on metallic surface, can to improve anticorrosive metal performance.
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| CN105215346A (en) * | 2015-08-30 | 2016-01-06 | 常州市鼎日环保科技有限公司 | A kind of preparation method being attached to ironing surface graphene oxide anticorrosive coat |
| CN105842318A (en) * | 2016-03-25 | 2016-08-10 | 大连理工大学 | Preparation method and application of graphene/polypyrrole electrochemical sensor for trace-amount lead ion detection |
| CN105986302A (en) * | 2016-07-04 | 2016-10-05 | 常州大学 | Technique for preparing protective coating on copper surface |
| CN106191967A (en) * | 2016-07-04 | 2016-12-07 | 常州大学 | A kind of process of doped graphene in polypyrrole coating |
| CN106276874A (en) * | 2016-08-10 | 2017-01-04 | 安徽省宁国天成电工有限公司 | A kind of preparation method of heater Graphene |
| CN108822292A (en) * | 2018-07-03 | 2018-11-16 | 山东交通学院 | A kind of preparation method and application of PbS point enhancing polypyrrole based composites |
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| CN111058078A (en) * | 2019-12-30 | 2020-04-24 | 中国科学院青海盐湖研究所 | Copper foil with graphene film coated on surface and preparation method thereof |
| CN111636085A (en) * | 2020-06-10 | 2020-09-08 | 深圳大学 | Anticorrosive coating and preparation method thereof |
| CN111850657A (en) * | 2020-07-30 | 2020-10-30 | 苏州科技大学 | Preparation method and application of polypyrrole/phytic acid/graphene oxide composite anti-corrosion coating |
| CN113318607A (en) * | 2021-04-30 | 2021-08-31 | 西安理工大学 | Preparation method of hydrophilic conductive polymer ultrafiltration membrane |
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| CN105842318A (en) * | 2016-03-25 | 2016-08-10 | 大连理工大学 | Preparation method and application of graphene/polypyrrole electrochemical sensor for trace-amount lead ion detection |
| CN105986302A (en) * | 2016-07-04 | 2016-10-05 | 常州大学 | Technique for preparing protective coating on copper surface |
| CN106191967A (en) * | 2016-07-04 | 2016-12-07 | 常州大学 | A kind of process of doped graphene in polypyrrole coating |
| CN106191967B (en) * | 2016-07-04 | 2019-01-25 | 常州大学 | A kind of process of the doped graphene in polypyrrole coating |
| CN106276874A (en) * | 2016-08-10 | 2017-01-04 | 安徽省宁国天成电工有限公司 | A kind of preparation method of heater Graphene |
| SE545567C2 (en) * | 2018-04-19 | 2023-10-24 | Provexa Ab | Method for surface treatment |
| CN108822292B (en) * | 2018-07-03 | 2020-09-08 | 山东交通学院 | Preparation method and application of PbS point reinforced polypyrrole-based composite material |
| CN108822292A (en) * | 2018-07-03 | 2018-11-16 | 山东交通学院 | A kind of preparation method and application of PbS point enhancing polypyrrole based composites |
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| CN111058078A (en) * | 2019-12-30 | 2020-04-24 | 中国科学院青海盐湖研究所 | Copper foil with graphene film coated on surface and preparation method thereof |
| CN111058078B (en) * | 2019-12-30 | 2021-09-24 | 中国科学院青海盐湖研究所 | Copper foil with graphene film coated on surface and preparation method thereof |
| CN111636085A (en) * | 2020-06-10 | 2020-09-08 | 深圳大学 | Anticorrosive coating and preparation method thereof |
| CN111850657A (en) * | 2020-07-30 | 2020-10-30 | 苏州科技大学 | Preparation method and application of polypyrrole/phytic acid/graphene oxide composite anti-corrosion coating |
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