CN104629585A - Anticorrosive paint taking rare earth cerium ion modified polyaniline hollow microspheres as additive - Google Patents
Anticorrosive paint taking rare earth cerium ion modified polyaniline hollow microspheres as additive Download PDFInfo
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- CN104629585A CN104629585A CN201510056309.7A CN201510056309A CN104629585A CN 104629585 A CN104629585 A CN 104629585A CN 201510056309 A CN201510056309 A CN 201510056309A CN 104629585 A CN104629585 A CN 104629585A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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Abstract
The invention discloses an anticorrosive paint taking rare earth cerium ion modified polyaniline hollow microspheres as an additive. The anticorrosive paint consists of epoxy resin, polyaniline hollow microspheres with rare earth cerium ions loaded on surfaces, a diluent, an auxiliary agent and a curing agent according to certain proportions. A coating layer prepared on surfaces of steel and an alloy material thereof by virtue of curing molding according to the formula of the anticorrosive paint is good in anticorrosive effect, is environment-friendly and has a very good application prospect in the field of steel material corrosion protection.
Description
Technical field
The present invention relates to the protective system that a kind of hollow polyaniline microspheres modified with rare-earth cerium ion is additive, belong to metallic substance corrosion-resistant field.
Background technology
Steel corrosion is the major issue be concerned always, and therefore people also have employed diverse ways to prevent the generation of corrosion.Wherein, the inhibiter containing chromium shows significant preservative effect on iron and steel and alloy, but chromic salts is containing toxic and carinogenicity, and this also greatly limit its application.At present, many report rare-earth cerium ions are had to have good slow release effect, cerium salt containing rare-earth cerium ion can as the inhibiter of iron and steel and alloy, and cerium ion has the characteristics such as efficient, nontoxic, environmental friendliness, and China's rare earth resources is abundant, cheap, develop rare earth resources fully, efficiently significant.
Polyaniline is a kind of important conductive polymers, have higher electroconductibility, preferably environmental stability and prepare easy, showing huge application potential in fields such as semiconductor material, battery, ultracapacitor, electromagnetic shielding material, sensing and corrosion protection coatings.At present, existing many relevant polyanilines and polyaniline zinc powder matrix material thereof are for the patent of corrosion-resistant field and document.But the antiseptic power of polyaniline itself is limited in these reports, comparatively significant preservative effect after adding a large amount of zinc powder, could be produced.Not only consume a large amount of metal zincs, also some adverse influences have been created to environment.Therefore, the Design & preparation of efficient, environmentally friendly polyaniline anti-corrosive paint is still a very important trend.
Summary of the invention
For polyaniline compound composite anti-corrosive coating of the prior art exist antiseptic power limited, consume a large amount of zinc powder and to deficiencies such as environment are friendly not, the object of the invention is to be to provide a kind of to iron and steel and better, the environment amenable hollow polyaniline microspheres modified using rare-earth cerium ion of the steel and alloy class material antiseptic effect protective system as additive.
The invention provides the protective system that a kind of hollow polyaniline microspheres modified with rare-earth cerium ion is additive, this protective system is made up of following mass percent component: epoxy resin 45 ~ 55%, area load has the hollow polyaniline microspheres 1 ~ 10% of rare-earth cerium ion, thinner 20 ~ 25%, auxiliary agent 0.3 ~ 0.5%, solidifying agent 15 ~ 25%.
In preferred protective system, area load has the hollow polyaniline microspheres external diameter of rare-earth cerium ion to be 340 ~ 420nm, and internal diameter is 220 ~ 260nm, and specific conductivity is 8.95 ~ 47.46S/cm, and the mass percent of trivalent cerium ion is 5 ~ 30%.
In preferred protective system, area load has the hollow polyaniline microspheres of rare-earth cerium ion to prepare by the following method: aniline is prepared hollow polyaniline microspheres by self-assembly method in the solution containing poly-(2-acrylamide-2-methylpro panesulfonic acid), hollow polyaniline microspheres obtains the hollow polyaniline microspheres that area load has rare-earth cerium ion stir doping in cerous nitrate (III) solution after.
Further preferred area load has the preparation method of the hollow polyaniline microspheres of rare-earth cerium ion: will gather (2-acrylamide-2-methylpro panesulfonic acid) and aniline joins in ethanol/water mixed solvent, mix, obtain mixing solutions, the mass percent of mixing solutions consists of: poly-(2-acrylamide-2-methylpro panesulfonic acid) 0.5 ~ 4.9%, aniline 2.2 ~ 2.5%, ethanol 7.4 ~ 7.8%, water 84.8 ~ 89.9%; After gained mixed solution is warming up to 50 ~ 80 DEG C, add the ammonium persulfate aqueous solution that temperature is 50 ~ 80 DEG C fast, after holding temperature reaction 1 ~ 2min, adjust the temperature to 0 ~ 5 DEG C of reaction 4 ~ 12h further immediately; Breakdown of emulsion, washing, the hollow polyaniline microspheres obtained; Gained hollow polyaniline microspheres is placed in cerous nitrate (III) solution that mass percent concentration is 0.057 ~ 2.79%, doping 4 ~ 12h is stirred at 25 ~ 50 DEG C of temperature, suction filtration, washing, drying, obtain the hollow polyaniline microspheres that area load has rare-earth cerium ion.
Preferred protective system epoxy resin is E-51 or E-44, is commercially available regular industrial level product.
In preferred protective system, thinner is made up of according to mass ratio 2 ~ 3:1 dimethylbenzene and propyl carbinol.Most preferably be and be made up of according to mass ratio 2.37:1 dimethylbenzene and propyl carbinol.
In preferred protective system, auxiliary agent is BYK-306; Can buy in German Bi Ke chemical company.
In preferred protective system, solidifying agent is polyamide 6 51; For commercially available regular industrial level product.
Compared with prior art, beneficial effect of the present invention: area load has the hollow polyaniline microspheres of rare-earth cerium ion to be applied to ferrous materials anticorrosion paint formulation as anticorrosive packing by the present invention first, obtains corrosion protection coating Iorn steel and alloy to fine preservative effect.Area load has rare-earth cerium ion and the polyaniline perfect adaptation of trivalent in the hollow polyaniline microspheres of rare-earth cerium ion, is added in steel anti-corrosive coating, and the antiseptic power of corrosion protection coating obtains obvious lifting.As tested data presentation (as table 1), load has the paint film adhesion of the anticorrosive polyaniline coating of rare-earth cerium ion to be 1 grade, but corrosion potential has brought up to-0.376V, all high than epoxy coat and polyaniline coating, corrosion current density has but been 10
-4μ A/cm
2rank.The measured result of corrosion protection coating in 3.5%NaCl solution also shows and with the addition of area load and have the protective system of the hollow polyaniline microspheres additive of rare-earth cerium ion to have good preservative effect.The present invention with the addition of area load has the protective system of the hollow polyaniline microspheres additive of rare-earth cerium ion to have wide application market at iron and steel and alloy corrosion-resistant field.
Accompanying drawing explanation
[Fig. 1] has the scanning electron microscope diagram of the hollow polyaniline microspheres of rare-earth cerium ion, energy spectrum analysis figure and transmission electron microscope figure: a to be scanning electron microscope (SEM) photograph under 20,000 multiplying powers for the embodiment of the present invention 1 obtains area load; B is the scanning electron microscope (SEM) photograph under 100,000 multiplying powers; C corresponds to the energy spectrum analysis in a in rectangular area; D is transmission electron microscope picture.
[Fig. 2] has the infrared spectrogram of the hollow polyaniline microspheres of rare-earth cerium ion for area load that embodiment 1 is obtained.
[Fig. 3] has the x-ray photoelectron spectroscopy analysis chart of the hollow polyaniline microspheres of rare-earth cerium ion for area load that embodiment 1 is obtained.
The area load that [Fig. 4] obtains for embodiment 1 has electroconductibility and the impedance chart of the hollow polyaniline microspheres of rare-earth cerium ion: a is conductivity map; B is impedance chart.
The area load that with the addition of that [Fig. 5] obtains for the embodiment of the present invention 3 and 5 and comparative example 2 has the scanning electron microscope diagram of the corrosion protection coating of the hollow polyaniline microspheres additive of rare-earth cerium ion: a with the addition of the scanning electron microscope (SEM) photograph that 1% area load has the corrosion protection coating of the hollow polyaniline microspheres additive of rare-earth cerium ion; B with the addition of the scanning electron microscope (SEM) photograph that 5% area load has the corrosion protection coating of the hollow polyaniline microspheres additive of rare-earth cerium ion; C with the addition of the scanning electron microscope (SEM) photograph that 10% area load has the corrosion protection coating of the hollow polyaniline microspheres additive of rare-earth cerium ion; D with the addition of the scanning electron microscope (SEM) photograph that 15% area load has the corrosion protection coating of the hollow polyaniline microspheres additive of rare-earth cerium ion.
[Fig. 6] has the hollow polyaniline microspheres of rare-earth cerium ion to be mixed with the optical picture of corrosion protection coating and the obtained anticorrosive test (720h) of PANI in iron-based material of comparative example 1 for area load that embodiment 3 is obtained: a is PANI; B is PANI/Ce
3+.
Embodiment
Following specific embodiment is intended to further illustrate content of the present invention, and unrestricted the scope of protection of the invention.
Embodiment 1
Get 6.32g dehydrated alcohol, the aqueous solution that 72.00g water, 2.08g contain poly-(2-acrylamide-2-methylpro panesulfonic acid) (being called for short PAMPS, massfraction 20%) joins in 250mL beaker, stir.Add 1.86g aniline subsequently in above-mentioned mixed solution, after ultrasonic 10min, the above-mentioned mixture system containing aniline is warming up to 80 DEG C, and magnetic agitation 10min at this temperature.Be 80 DEG C by temperature, the aqueous solution of the 40mL containing 4.56g ammonium persulphate adds in the above-mentioned mixed solution containing aniline fast, under agitation constant temperature 80 DEG C reaction 60s.Be in the ice-water bath of 0-5 DEG C, continue reaction 12h subsequently by reaction system transposition temperature.Use acetone breakdown of emulsion, washing, suction filtration, obtain hollow polyaniline microspheres.Joined by the hollow polyaniline microspheres obtained in the 50mL aqueous solution containing 0.36g cerous nitrate (III), room temperature lower magnetic force stirs 12h, and suction filtration, washing, drying obtain the hollow polyaniline microspheres that area load has rare-earth cerium ion.Carry out specific surface area test, specific surface area is 9.68m
2/ g.
The area load of the electron scanning micrograph display preparation of Fig. 1 has the polyaniline microsphere external diameter of rare-earth cerium ion to be about 380nm, the area load that transmission electron microscope figure shows preparation has the polyaniline microsphere of rare-earth cerium ion to present hollow structure, and wall thickness is about about 67nm, ball internal diameter is about about 244nm.
Fig. 2 is the infrared spectrogram that area load has the polyaniline microsphere of rare-earth cerium ion.1562cm
-1and 1490nm
-1be respectively quinone ring and the phenyl ring characteristic peak of polyaniline, confirm the existence of polyaniline.1645cm
-1for PAMPS characteristic peak.1142cm
-1for C-N telescope features peak, after rare earth doped cerium ion, this characteristic peak broadens, at 1105cm
-1place also occurs that peak position illustrates that cerium ion and electron rich N there occurs synergy.
Fig. 3 is the x-ray photoelectron spectroscopy data that area load has the hollow polyaniline microspheres of rare-earth cerium ion, and wherein the appearance of cerium ion peak position also demonstrate that hollow polyaniline microspheres successfully adulterates load cerium ion.
The area load that Fig. 4 is prepared position has specific conductivity and the impedance data of the hollow polyaniline microspheres of rare-earth cerium ion, the percentage composition that result demonstrates along with cerium ion increases, the specific conductivity of hollow microsphere is increased to 46.76S/cm from 8.95S/cm always, and the charge-transfer resistance (arc radius) that impedance spectrum also shows microballoon also reduces gradually.
Table 1 is the energy spectrum analysis data of Fig. 1 (c)
| Element | wt％ | wt％Sigma |
| C | 72.05 | 0.61 |
| N | 13.40 | 0.68 |
| O | 10.56 | 0.24 |
| S | 3.12 | 0.05 |
| Ce | 0.88 | 0.05 |
| Total amount: | 100.00 |
Embodiment 2
Get 6.32g dehydrated alcohol, the aqueous solution that 72.00g water, 2.08g contain poly-(2-acrylamide-2-methylpro panesulfonic acid) (being called for short PAMPS, massfraction 40%) joins in 250mL beaker, stir.Add 1.86g aniline subsequently in above-mentioned mixed solution, after ultrasonic 10min, the above-mentioned mixture system containing aniline is warming up to 65 DEG C, and magnetic agitation 10min at this temperature.Be 65 DEG C by temperature, the aqueous solution of the 40mL containing 4.56g ammonium persulphate adds in the above-mentioned mixed solution containing aniline fast, under agitation constant temperature 65 DEG C reaction 80s.Be in the ice-water bath of 0-5 DEG C, continue reaction 6h subsequently by reaction system transposition temperature.Use acetone breakdown of emulsion, washing, suction filtration, obtain hollow polyaniline microspheres.Joined by the hollow polyaniline microspheres obtained in the 50mL aqueous solution containing 0.18g cerous nitrate (III), room temperature lower magnetic force stirs 8h, and suction filtration, washing, drying obtain the hollow polyaniline microspheres that area load has rare-earth cerium ion.Carry out specific surface area test, specific surface area 9.55m
2/ g.
Embodiment 3
The polyaniline microsphere of rare-earth cerium ion is had for ferrous materials anticorrosion paint formulation with the area load that embodiment 1 is obtained:
Take 15.0g E-51 epoxy resin respectively, 4.5g dimethylbenzene, 1.9g propyl carbinol and 0.12g flow agent BYK-306 mix at room temperature 35 ~ 40 DEG C, the hollow polyaniline microspheres of rare-earth cerium ion is had by the area load of 1.1g to join in above-mentioned epoxy mixed solution, after stirring, add in conoidal mill, grind and obtain component A 3 times.6.0g B component (solidifying agent polyamide 6 51) is joined in above-mentioned component A, obtains after stirring with the addition of the hollow polyaniline microspheres protective system that area load has rare-earth cerium ion.By anti-corrosion paint obtained above in steel surface (area 1.0 × 1.0cm
2), coating thickness controls at 40 ± 5 μm for electro-chemical test.Be 15.0 × 7.0cm by size in addition
2iron plate also apply coating, coating thickness controls at 200 ± 10 μm, and two mutually perpendicular length are 8.0cm on central zone is drawn, and width is that the straight line of 0.5cm is soaked in 3.5% sodium chloride brine and carries out erosion resistance experiment.
What Fig. 5 (b) was prepared for embodiment 3 with the addition of the scanning electron microscope diagram sheet that area load has the corrosion protection coating of the hollow polyaniline microspheres of rare-earth cerium ion, and the surfacing of coating as seen from the figure occurs without hollow phenomenon.In addition, the sticking power that the paint film adhesion test result of table 2 shows this coating is 1 grade, shows that the sticking power of coating is better.The data of table 2 also show and with the addition of area load and have the corrosion potential of the hollow polyaniline microspheres corrosion protection coating of rare-earth cerium ion to be-0.376V, than the height of the corrosion protection coating of single interpolation hollow polyaniline microspheres, the corrosion current density of coating has been reduced to 1.256 × 10
-4μ A/cm
2.The measured result of Fig. 6 also shows and with the addition of area load and have the anti-corrosion effects of the corrosion protection coating of the hollow polyaniline microspheres of rare-earth cerium ion better, cerium ion add the very large resistance to corrosion enhancing coating.
Table 2 has the performance test data of the protective system of the hollow polyaniline microspheres of rare-earth cerium ion for area load
Embodiment 4
The hollow polyaniline microspheres of rare-earth cerium ion is had for ferrous materials anticorrosion paint formulation with the area load that embodiment 2 is obtained:
Take 13.0g E-51 epoxy resin respectively, 4.5g dimethylbenzene, 1.9g propyl carbinol and 0.09g flow agent BYK-306 mix at room temperature 35 ~ 40 DEG C, the hollow polyaniline microspheres of rare-earth cerium ion is had by the area load of 1.5g to join in above-mentioned epoxy mixed solution, after stirring, add in conoidal mill, grind and obtain component A 3 times.5.0g B component (solidifying agent polyamide 6 51) is joined in above-mentioned component A, obtains after stirring with the addition of the protective system that area load has the hollow polyaniline microspheres of rare-earth cerium ion.Paint film adhesion test result display sticking power is 1 grade, and the corrosion potential of Electrochemical results display coating is-0.354V, and corrosion current density is still 10
-4μ A/cm
2rank, the resistance to corrosion of coating is better.
Embodiment 5
The hollow polyaniline microspheres of rare-earth cerium ion is had for ferrous materials anticorrosion paint formulation with the area load that embodiment 1 is obtained:
Take 15.0g E-51 epoxy resin respectively, 4.5g dimethylbenzene, 1.9g propyl carbinol and 0.12g flow agent BYK-306 mix at room temperature 35 ~ 40 DEG C, the hollow polyaniline microspheres of rare-earth cerium ion is had by the area load of 3.06g to join in above-mentioned epoxy mixed solution, after stirring, add in conoidal mill, grind and obtain component A 3 times.6.0g B component (solidifying agent polyamide 6 51) is joined in above-mentioned component A, obtains after stirring with the addition of the protective system that area load has the hollow polyaniline microspheres of rare-earth cerium ion.Paint film adhesion test result display sticking power is 1 grade, and the corrosion potential of Electrochemical results display coating is-0.348V, and corrosion current density is still 10
-4μ A/cm
2rank, coatingsurface is hollow slightly; As shown in Fig. 5 (c), but overall more smooth, and the resistance to corrosion of coating is better.
Comparative example 1
Take 15.0g E-51 epoxy resin respectively, 4.5g dimethylbenzene, 1.9g propyl carbinol and 0.12g flow agent BYK-306 mix at room temperature 35 ~ 40 DEG C, 1.1g hollow polyaniline microspheres (not containing rare-earth cerium ion) is joined in above-mentioned epoxy mixed solution, after stirring, add in conoidal mill, grind and obtain component A 3 times.6.0g B component (solidifying agent polyamide 6 51) is joined in above-mentioned component A, after stirring, obtains the protective system being added with hollow polyaniline microspheres.By anti-corrosion paint obtained above in steel surface (area 1.0 × 1.0cm
2), coating thickness controls at 40 ± 5 μm for electro-chemical test.Be 15.0 × 7.0cm by size in addition
2iron plate also apply coating, coating thickness controls at 200 ± 10 μm, and two mutually perpendicular length are 8.0cm on central zone is drawn, and width is that the straight line of 0.5cm is soaked in 3.5% sodium chloride brine and carries out erosion resistance experiment.
The corrosion potential of the data presentation corrosion protection coating of table 2 is-0.522V, and the corrosion current density of coating is 1.318 × 10
-4μ A/cm
2.The anti-corrosion effects that the measured result of Fig. 6 also shows the corrosion protection coating that with the addition of hollow polyaniline microspheres has the hollow polyaniline microspheres preservative effect of rare-earth cerium ion not as good as area load.
Comparative example 2
Take 15.0g E-51 epoxy resin respectively, 4.5g dimethylbenzene, 1.9g propyl carbinol and 0.12g flow agent BYK-306 mix at room temperature 35 ~ 40 DEG C, 4.86g area load embodiment 1 prepared has the hollow polyaniline microspheres of rare-earth cerium ion to join in above-mentioned epoxy mixed solution, after stirring, add in conoidal mill, grind and obtain component A 3 times.6.0g B component (solidifying agent polyamide 6 51) is joined in above-mentioned component A, after stirring, obtains the protective system that with the addition of hollow polyaniline microspheres.By anti-corrosion paint obtained above in steel surface (area 1.0 × 1.0cm
2), coating thickness controls at 40 ± 5 μm for electro-chemical test.
It is-0.311V that electrochemical test data shows this corrosion potential that with the addition of the corrosion protection coating of hollow polyaniline microspheres, and the corrosion current density of coating is 1.349 × 10
-4μ A/cm
2.But Fig. 5 (d) shows coatingsurface unfairness.
Claims (7)
1. the protective system that the hollow polyaniline microspheres modified with rare-earth cerium ion is additive, is characterized in that, be made up of following mass percent component:
Epoxy resin 45 ~ 55%,
Area load has the hollow polyaniline microspheres 1 ~ 10% of rare-earth cerium ion,
Thinner 20 ~ 25%,
Auxiliary agent 0.3 ~ 0.5%,
Solidifying agent 15 ~ 25%.
2. protective system according to claim 1, it is characterized in that, described area load has the hollow polyaniline microspheres external diameter of rare-earth cerium ion to be 340 ~ 420nm, and internal diameter is 220 ~ 260nm, specific conductivity is 8.95 ~ 47.46S/cm, and the mass percent of trivalent cerium ion is 5 ~ 30%.
3. protective system according to claim 1 and 2, it is characterized in that, described area load has the hollow polyaniline microspheres of rare-earth cerium ion to prepare by the following method: aniline is prepared hollow polyaniline microspheres by self-assembly method in the solution containing poly-(2-acrylamide-2-methylpro panesulfonic acid), hollow polyaniline microspheres obtains the hollow polyaniline microspheres that area load has rare-earth cerium ion stir doping in cerous nitrate (III) solution after.
4. protective system according to claim 1, is characterized in that, described epoxy resin is E-51 or E-44.
5. protective system according to claim 1, is characterized in that, described thinner is made up of according to mass ratio 2 ~ 3:1 dimethylbenzene and propyl carbinol.
6. protective system according to claim 1, is characterized in that, described auxiliary agent is BYK-306.
7. protective system according to claim 1, is characterized in that, described solidifying agent is polyamide 6 51.
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| CN112592652A (en) * | 2020-12-01 | 2021-04-02 | 北京联合大学 | Preparation method of polyaniline/cerium nitrate/epoxy polymer coating |
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