CN105238207B - A kind of conductive multifunctional anticorrosive coating of high performance super-amphiphobic and preparation method thereof - Google Patents
A kind of conductive multifunctional anticorrosive coating of high performance super-amphiphobic and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of conductive multifunctional anticorrosive coating of high performance super-amphiphobic.It is characterized in that：Including bottom and two, top layer component, the bottom component is epoxy resin and epoxy curing agent, organic fluorine, polyaniline/carbon nano-fiber composite material；The top layer component is organic fluorine, Nano filling, the silicon fluoride coupling agent of low-surface-energy modification.The conductive multifunctional anticorrosive coating of the high performance super-amphiphobic, can be provided simultaneously with the characteristics of super-amphiphobic, drag-reducing abrasion-resisting, resistance to pitting, with low cost.Present invention also offers a kind of preparation method of the conductive multifunctional anticorrosive coating of high performance super-amphiphobic.
Description
Technical field
The present invention relates to the conductive multifunctional anticorrosive coating preparation field of super-amphiphobic, more particularly to one kind is in petroleum chemical industry
In there is coating of super-hydrophobic, superoleophobic, drag-reducing abrasion-resisting and excellent pitting corrosion resistance and preparation method thereof.
Background technology
Corrosion is that the perforation leakage of a great problem for perplexing petroleum chemical industry, particularly oil pipeline and storage tank not only can
Have a strong impact on oil field normally to produce, cause huge economic loss and security incident, and society and environment can also be produced sternly
The consequence of weight.The preservative mechanism of traditional insulation organic coating is shielding action, once there is pin hole or breakage on coating, will
Form the corrosion cell of big negative electrode primary anode so that corrosion concentrates on pin hole or breakage, accelerate the pitting speed of pipeline.
Organic polymer conductive polymer polyanaline（PANI）Constructed conductive coating is due to the passivation to metal surface
Effect and electric field action, the resistance to pitting hardly matched with insulating coating, scratch resistance capability.Chinese patent CN102702920B
（A kind of Waterborne Polyaniline Corrosion Protection Coatings and preparation method thereof）、CN102702815B（A kind of UV Curing Anti-Corrosive Coatings）、
CN102702467B（Waterborne polyurethane resin, Waterborne Polyaniline Corrosion Protection Coatings and preparation method thereof）、CN102643592B（Polyphenyl
The preparation method of amine modified mesoporous molecular sieve anticorrosive paint）、CN102108241B（A kind of phosphate doped polyaniline anticorrosive paint
And preparation method thereof）Effective trial has all been carried out to anticorrosive polyaniline coating.
But, layer/polyaniline conductive coating still suffers from two key issues in practical engineering application, seriously restricts its big rule
Mould is promoted and development.（1）The wearability of simple polyaniline coating, adhesive force and the drag reduction scale inhibition to fluid with metallic substrates
Etc. the demand that performance does not reach commercial Application still, especially tradition blending coated polyurethane, epoxy resin etc. are applied to profit
When fluid-mixing pipeline and equipment, it is impossible to meet the long-lasting protection demand of its drag-reducing abrasion-resisting scale inhibition for the hydrophily of coating；（2）It is poly-
Aniline is a kind of macromolecular of the big pi bond of conjugation with very strong interaction, and rigidity is big, and interchain hydrogen bond interaction is strong, dissolving
Property it is poor, the PANI of classical chemistry or electrochemistry formated is in amorphous powder, has a strong impact on its dispersing uniformity in the coating
And processing characteristics.
Bionic super-hydrophobic is superoleophobic（Super-amphiphobic）Surface can effectively suppress diffusion of the corrosive substance to coat inside, pole
The earth improves the resistance to corrosion of coating, has broad application prospects.Present invention firstly provides by super-amphiphobic coating and polyphenyl
Amine conductive coating is coupled, and by simple process construct can while realize the corrosion-inhibiting coating of super-hydrophobic, superoleophobic, resistance to pitting,
With great industrial application value.
Existing super-amphiphobic coating still suffers from that adhesive force is low, worn no resistance, preparation technology complexity, expensive raw material price etc. are asked
Topic, such as A of Chinese patent CN 103408707 propose amphiphilic cross-linking fluorine silicon resin super-amphiphobic coating, and its floating coat is former
Expect amphipathic cross-linking fluorine silicon resin and need hydrogeneous organosilicon, containing epoxy, fluorine-containing material, improved silica and hydrophilic
Property material mixing in solvent, be added in reactor, and be passed through inert gas, stirred under the conditions of 60~140 DEG C, then add
Enter catalyst, be kept stirring for 5~24 h, then above-mentioned reactant is deposited in n-hexane or methanol obtained.The preparation work being related to
Skill is cumbersome, severe reaction conditions；Chinese patent CN103881532 A propose the mixture of primary coat epoxy resin and curing agent, face
Modified nano-silver thread solution is applied, super-double-hydrophobic surface is prepared.But nano-silver thread cost is higher, preparation technology is complicated, and surface layer is wear-resisting
Property is poor.
The content of the invention
The invention reside in overcome existing super-amphiphobic coating present in background technology and the shortcoming of layer/polyaniline conductive coating and
Deficiency, and provide a kind of high performance super-amphiphobic conductive multifunctional anticorrosive coating.The high performance super-amphiphobic is conductive multi-functional anti-
Rotten coating, can be provided simultaneously with the characteristics of super-amphiphobic, drag-reducing abrasion-resisting, resistance to pitting, with low cost.Present invention also offers a kind of high
The preparation method and applications of the conductive multifunctional anticorrosive coating of the super-amphiphobic of performance.
The present invention, which solves its problem, to be reached by following technical solution：The high performance super-amphiphobic is conductive multi-functional anti-
Rotten coating, including bottom and two, top layer component, the bottom component are epoxy resin and epoxy curing agent, Organic fluoride tree
Fat, polyaniline/carbon nano-fiber composite material, silicon fluoride coupling agent；The top layer component is organic fluorine, low-surface-energy changes
Nano filling, silicon fluoride coupling agent, the organic solvent of property.
The bottom component and top layer constituent mass ratio are 1：(1~2)；The bottom epoxy resin, epoxy resin are solid
Agent, organic fluorine, polyaniline/carbon nano-fiber composite material, the mass ratio of organic solvent are 1：(0.1~0.2)：(0.1
~0.3)：(0.05~0.15)：(10~15)；Organic fluorine, Nano filling, the fluorine silicon of low-surface-energy modification in the top layer
Alkane coupling agent, the mass ratio of organic solvent are 1：(0.1~0.2)：(0.05~0.15)：(15~20).
It is a further object of the present invention to provide a kind of preparation method of the super-amphiphobic conductive coating based on above-mentioned performance, including
Following steps：
（1）Metal base surface is pre-processed
Sandblasting or shot-peening, polishing, cleaning and drying and processing are carried out to metal base surface；
（2）The preparation of coating bottom strata
Subbing is configured, by epoxy resin, epoxy curing agent dissolving in organic solvent, is stirred simultaneously
30 min are cured, organic fluorine and polyaniline/carbon nano-fiber composite material is sequentially added, the min of ultrasonic disperse 20, and
The min of magnetic agitation 20~30, that is, be made subbing；
In step（1）Sprayed layer undercoat coating on metallic matrix after processing, by the metallic matrix after spraying with 2~6 DEG C/
Min heating rate is warming up to 80~100 DEG C, and 1~2 h of solidification at a temperature of 80~100 DEG C；
（3）The preparation on coating top layer：
Successively by organic fluorine and the Nano filling of low-surface-energy modification, silicon fluoride coupling agent ultrasonic disperse organic molten
In agent, the min of magnetic agitation 20~30, then in above-mentioned steps（2）Continue to spray surface coating material on the bottom of preparation, will spray
Metallic matrix afterwards is warming up to 200~300 DEG C with 2~6 DEG C/min heating rate, and solid at a temperature of 200~300 DEG C
Change 1~2 h, be down to naturally after room temperature and obtain whole super-amphiphobic conductive coating.
The principle of the conductive multifunctional anticorrosive coating technology scheme of the high performance super-amphiphobic of the present invention：
1. polyaniline/carbon nano-fiber composite material
The mechanism for preparing polyaniline/carbon nano-fiber composite material using in-situ chemical polymerization is as follows：Carbon nano-fiber
The easily dispersed aniline monomer in aqueous, being dissolved in water is adsorbed in carbon nano-fiber table first after carboxylated processing
Face, then issues biochemical oxidative polymerization in the initiation of oxidant and inorganic acid, forms doped electrically conductive polyaniline.
In the polymerization process of aniline, carbon nano-fiber plays skeletal support effect, and aniline is slow around it using carbon nano-fiber to ride in
Slow polymerization, polyaniline molecule is combined closely with carbon nano-fiber by electrostatic interaction and π-π interactions, ultimately forms polyphenyl
Amine/carbon nano-fiber composite material.
The pi-pi accumulation structure existed between quinone ring structure on carbon nano-fiber and polyaniline backbone, can stablize polyphenyl
The quinoid structure of amine, strengthens the reversible electric conductivity of polyaniline.And carbon nano-fiber can form network with polyaniline composite material
Structure, the compatibility with organic matter is good, can significantly improve the electric conductivity and mechanical property of coating.
2. the reaction mechanism of Nano filling
The low-surface-energy modifying agent of described Nano filling is gamma-aminopropyl-triethoxy-silane, different containing two kinds
Active group amino and ethyoxyl, for being coupled organic polymer and inorganic filler, can improve the wetting of filler in the polymer
Property and dispersiveness, strengthen interface adhesion.Modified reaction mechanism includes：（1）The ethoxy hydrolysis being connected with silicon atom, it is raw
Into-Si-OH；（2）Dehydrating condensation between-Si-OH, oligosiloxane of the generation containing-Si-OH；（3）- Si- in oligosiloxane
The OH and hydroxyl-OH of inorganic filler surface formation hydrogen bonds；（4）In heat curing process, with dehydration with organic epoxy
Resin formation covalent bond connection, so as to improve the water ratio limit intensity of composite.
3. super-double-hydrophobic surface formation mechenism
The Nano filling being modified using low-surface-energy is dispersed in organic fluorine, and surface tension is reduced in coating surface
Nano/micron binary coarse structure is built simultaneously, forms the top layer of ultra-amphosphobic energy.
4. the Wear Resistance Mechanism of coating
The Nano filling that low-surface-energy is modified, which is dispersed in organic fluorine coat inside, can play the wear-resisting work of enhancing coating
With mechanism of action is：1. Nano filling produces stress concentration effect in friction process, plays coating toughening effect；2. receive
Rice filler will not produce big elongation strain under action of pulling stress, can be passivated coating crack；3. the ratio surface of Nano filling
Product is big, and the physics and chemical imperfection on surface are a lot, thus Nano filling and organic fluorine contact area it is big and by physics and
Chemical action is combined closely, can be with the impact energy in absorber coatings friction process, it is to avoid coating cracking, ensures the long-acting of coating
Wear-resisting ultra-amphosphobic energy.
The present invention is coated substrate using the organic fluorine of the excellent epoxy resin of adhesive force and low-surface-energy, using letter
The pressure-air spraying coating process of single easily scale prepares the conductive composite coating of super-amphiphobic.In addition, carbon nano-fiber has uniqueness
Structure, very high draw ratio, higher effective ratio area, good conduction, heat conduction and mechanical property, polyphenyl can be strengthened
The mechanics and electric conductivity of amine high molecular polymer.Prepared polyaniline/carbon nano-fiber composite material combines conductive height
The advantage of molecule and nano material, with the Wuli-Shili-Renli system approach not available for many macroscopic materials, such as dimensional effect, quantum
Effect, skin effect.Therefore, the present invention prepares polyaniline/carbon nano-fiber composite material as coated conductive filler, super double
Conductive network is built in open coat matrix, excellent antiseptic property can be realized.
It is of the invention to be had the advantages that compared with above-mentioned background technology：The conductive many work(of the high performance super-amphiphobic
Energy corrosion-inhibiting coating, bottom adhesive force is strong, resistance to pitting；Surface layer super-amphiphobic, wear-resisting drag reduction；Bottom adds a small amount of organic fluorine, can
With the organic fluorine crosslinking curing on top layer, it is ensured that the adhesion strength and compatibility of interlayer；The preparation technology letter that the present invention is used
Single, low in raw material price easily industrializes large-scale application.
Brief description of the drawings
Accompanying drawing 1 is the scanning electron microscope (SEM) photograph of polyaniline/carbon nano-fiber composite material in inventive embodiments 1；
Accompanying drawing 2 is the transmission electron microscope picture of polyaniline/carbon nano-fiber composite material in inventive embodiments 1；
Accompanying drawing 3 is the surface topography map of super-amphiphobic conductive coating in inventive embodiments 1；
Accompanying drawing 4 is contact angle figure of the super-amphiphobic conductive coating to water in inventive embodiments 1；
Accompanying drawing 5 is contact angle figure of the super-amphiphobic conductive coating to ethylene glycol in inventive embodiments 1；
Accompanying drawing 6 is contact angle figure of the super-amphiphobic conductive coating to glycerine in inventive embodiments 1；
Accompanying drawing 7 is contact angle figure of the super-amphiphobic conductive coating to crude oil in inventive embodiments 1；
Accompanying drawing 8 is electrokinetic potential pole of the super-amphiphobic conductive coating in 3.5 wt% NaCl etchant solutions in inventive embodiments 1
Change curve；
Accompanying drawing 9 is impedance diagram of the pure aluminum plate in 3.5 wt% NaCl etchant solutions in inventive embodiments 1；
Accompanying drawing 10 is impedance diagram of the super-amphiphobic conductive coating in 3.5 wt% NaCl etchant solutions in inventive embodiments 1.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described：
Embodiment 1：
Using nano silicon as Nano filling, with epoxy resin, ethylene-tetrafluoroethylene copolymer, PEP
Copolymer is coated substrate, on aluminium sheet prepare with excellent antiseptic property super-amphiphobic conductive coating, and strong acid, highly basic and
The antiseptic property of coating is detected in high salt concentration water environment.
（1）Carbon nano-fiber is modified
After 30mL concentrated nitric acids and the mixing of the 90mL concentrated sulfuric acids, 0.5g carbon nano-fibers are added, are heated with constant temperature blender with magnetic force
4 h are stirred to 80 DEG C and constant temperature, is cooled to after room temperature, neutrality is washed to distillation, are finally done in an oven under the conditions of 60 DEG C
Dry 24 h, obtains the carbon nano-fiber of carboxylated.
（2）The preparation of polyaniline/carbon nano-fiber composite material
The sulfuric acid solution that 1L concentration is 0.2mol/L is prepared, takes the carbon nano-fiber of 0.1g carboxylated to add to 500 mL sulphur
Acid solution（0.2 mol/L）In, the min of ultrasonic disperse 30；1 g aniline monomers are added into above-mentioned solution, the h of ultrasonic agitation 12；
2.5 g ammonium persulfates are taken to be dissolved to 500 mL sulfuric acid solutions（0.2 mol/L）In, quickly mixed with aniline/carbon nano-fiber solution
Close, carrying out chemical oxidising polymerisation under the conditions of 0~4 DEG C after the min of ultrasonic disperse 30 reacts 24 h, then by the sediment of generation
Neutrality is washed till with distilled water and ethanol suction filtration, 24 h is dried under the conditions of 60 DEG C in an oven, obtains blackish green polyaniline/carbon and receive
Rice fibrous composite.
（3）The preparation for the Nano filling that low-surface-energy is modified
Sequentially add ethanol 36mL, water 2mL, gamma-aminopropyl-triethoxy-silane 2mL and mixed liquor is made, use constant temperature magnetic force
Agitator is heated to 50 DEG C and constant temperature stirs 30 min；0.2 g nano silicons are added in above-mentioned mixed liquor（Particle diameter is about
For 50 nm）, constant temperature stirs 24 h under the conditions of 50 DEG C；Modified inorganic nano-filler is cleaned with distillation water filtration, most
Dry 24 h under the conditions of 60 DEG C in an oven afterwards.
（4）It is prepared by coating
The pretreatment of metal base：Area is regard as substrate, establishing criteria for 8cm × 8cm aluminium sheet《Steel table before application
Face rusting grade and derusting grade》（GB 8923-88）, St3 is polishing to step by step with 360 mesh, 600 mesh and 1000 mesh sand paper respectively
Level standard.Deionized water rinsing is used after polishing, oil removing is cleaned with acetone and dries；
The preparation of coating bottom strata：The area applied with one side, takes 1g bisphenol A type epoxy resins（E-44）, many amines of 0.2g
Curing agent dissolves in organic solvent, stirs and cures 30 min, then sequentially adds 0.2 g ethene-tetrafluoro second
Alkene copolymer and polyaniline/carbon nano-fiber composite material, the min of ultrasonic disperse 20, and the min of magnetic agitation 20~30；Will system
Standby subbing is sprayed into pretreated substrate surface, and spray distance is 12~15 cm, and air pressure is 0.5 bar, with 2~6
DEG C/min heating rate is warming up to 80 DEG C, solidifies 1 h under the conditions of 80 DEG C；
The preparation on coating top layer：Take 1g ethylene-tetrafluoroethylene copolymers, 0.5g fluorinated ethylene propylene copolymers, 0.15 g
The nano silicon and 0.1 g silicon fluoride coupling agent ultrasonic disperses that low-surface-energy is modified are in 20 mL ethyl acetate, and magnetic force is stirred
Sprayed after mixing 30 min as surface coating material, spray distance is 12~15 cm, air pressure is 0.5 bar, in an oven finally
300 DEG C are warming up to 2~6 DEG C/min heating rate, and solidifies 2 h under the conditions of 300 DEG C, is down to after room temperature and obtains naturally
To super-amphiphobic top layer.
（5）Performance test and effect
Coating morphology and composition test and result：Found using SEM and transmission electron microscope observing, polyaniline
Growth in situ is realized on carbon nano-fiber surface, polyaniline/carbon nano-fiber composite material is such as attached in network fibres structure is intersected
Shown in Fig. 1 and Fig. 2；The electrical conductivity of polyaniline/carbon nano-fiber composite material is 3.5 S/cm；Prepared super-amphiphobic conduction is applied
Layer surface is Nano/micron diadactic structure, as shown in Figure 3；
Super-amphiphobic performance test and result：Coating is measured to water, ethylene glycol, glycerine and original using Static Contact angle measuring instrument
The contact angle of oil is respectively 168 °, 159 °, 156 ° and 155 °, to oil water mixture（Crude oil is 1 with water volume ratio：9）Rolling
Angle be 5 °, as shown in accompanying drawing 4, Fig. 5, Fig. 6, Fig. 7, thus the coating can realize it is super-hydrophobic, superoleophobic, for oil water mixture
Fluid line reduces the attachment of coating surface pollutant, realizes that drag-reducing abrasion-resisting has unique advantage.
Adhesive force is tested and result：According to standard GB/T/T9286-1998《The cross cut test of paint and varnish paint film》,
Penetrated with cartesian mesh pattern cut coating to ground, the coating cut edge prepared by this example is completely smooth, none lattice takes off
Fall, therefore this coating has reached optimal 0 grade of adhesion effect.
Wearability test and result：Prepared coating is rubbed repeatedly with 1000 mesh sand paper, test pressure is 10
N, after being rubbed through 10000 times, coating is not galled, and coating hydrophobic angle remains at 158 °, the contact to glycerine with crude oil
Angle is maintained at 152 and 151 °, to oil water mixture（Crude oil and water volume ratio are 9：1）Roll angle be 9 °, illustrate that coating is wear-resisting
Excellent performance, and through long-time rub after remain to keep ultra-amphosphobic energy.
Acid-alkali-corrosive-resisting is tested and result：Prepared super-amphiphobic coating is soaked in strong acid（pH=1）And highly basic（pH=
14）30 days in solution, using SEM（SEM）Apparent form is observed, it is found that coating still is able to holding and receives micro- binary
Rustic degree；The hydrophobic angle of coating after being soaked in strong acid and highly basic is respectively 153 ° and 151 °, to the contact angle of crude oil
Respectively 149 ° and 145 °, show that coating still is able to keep super-hydrophobic well and oleophobic performance, the coating can be applied to real
In the corrosive environment on border.
Electrochemical corrosion protection test and result：Super-amphiphobic conductive coating will be scribbled and be soaked in 3.5% NaCl corrosive mediums
In 120 days, measure its OCP, ac impedance spectroscopy and dynamic potential polarization curve.It is sweet with saturation using platinum plate electrode as to electrode
Mercury electrode is reference electrode, and test is carried out at ambient temperature.Dynamic potential polarization curve figure shows to apply as shown in Figure 8, as a result
Layer is immersing 120 days post-etching potentials（Ecorr）358 mV are shuffled than pure aluminum plate, corrosion current declines about 3 numbers than pure aluminum plate
Magnitude, it is 99.9% that corrosion protection efficiency high, which reaches,；Ac impedance spectroscopy（See accompanying drawing 9, Figure 10）As a result show pure aluminum plate in immersion 30
Pitting occurs after min, and the aluminium sheet of super-amphiphobic conductive coating protection still keeps excellent antiseptic property after soaking 120 days, says
The bright coating has excellent long-effective corrosion ability to aluminium sheet.
Embodiment 2：
Using nano molybdenum disulfide as filler, using epoxy resin, poly- inclined tetrafluoroethene, fluorinated ethylene propylene copolymer as coating
Matrix, prepares the conductive corrosion-inhibiting coating of super-amphiphobic on steel plate.
Prepared by the step of according to embodiment 1, be with the difference of embodiment 1：
Step（1）Concentration of the middle carbon nano-fiber in mixed acid solution is 3mg/mL；
Step（2）The mass ratio of middle aniline and the carbon nano-fiber of carboxylated is 1：0.2；
Step（3）Middle Nano filling uses nano molybdenum disulfide, and particle diameter is about 80nm, and concentration is 3mg/mL；
Step（4）Floating coat choice of the substrates petroleum pipeline often uses the steel plate of sheet material X80 materials；Linear aliphatic in subbing
Same clan's epoxy resin, polyamide-based curing agent, poly- inclined tetrafluoroethene, polyaniline/carbon nano-fiber composite material, ethyl acetate are molten
The mass ratio of agent is 1：0.15：0.2：0.1：15；Investment precoat selects Kynoar, fluorinated ethylene propylene copolymer, low table
Nano molybdenum disulfide that face can be modified, silicon fluoride coupling agent, the mass ratio of ethyl acetate solvent are 1：0.3：0.15：0.1：20；
Step（5）Floating coat the performance test results are：The electrical conductivity of polyaniline/carbon nano-fiber composite material is 3.8 S/
cm；Coating is respectively 169 °, 158 °, 157 ° and 154 ° to the contact angle of water, ethylene glycol, glycerine and crude oil, to oil water mixture
（Crude oil is 1 with water volume ratio：9）Roll angle be 4 °, illustrate that the coating can be realized super-hydrophobic, superoleophobic；Adhesive force is tested
As a result show that coating adhesion effect belongs to optimal 0 grade of adhesion effect；Frictional experiment result is to be dredged after coating rubs through 10000 times
Water angle is 157 °, and the contact angle to glycerine and crude oil is 153 ° and 151 °, to oil water mixture（Crude oil and water volume ratio are 1：9）
Roll angle be 8 °, illustrate that coating wear resistance is excellent, and by for a long time friction after can keep ultra-amphosphobic energy；Coating
In strong acid（pH=1）And highly basic（pH=14）After middle immersion 90 days, hydrophobic angle is 154 ° and 152 °, is respectively to the contact angle of crude oil
150 ° and 148 °, show that coating has stable super-hydrophobic and oleophobic performance in actual corrosive environment；Electrochemical anti-corrosive performance
Test result shows that the open circuit potential of coating is shuffled than clean steel plate after coating soaks 120 days in 3.5% NaCl corrosive mediums
375 mV, corrosion protection speed is 99.9%, and ac impedance spectroscopy shows that etchant solution does not enter into coat inside, illustrates the coating
There is excellent long-lasting protection ability to base material.
Claims (8)
1. a kind of conductive multifunctional anticorrosive coating of high performance super-amphiphobic, it is characterised in that：Including bottom and two, top layer component,
The bottom component be epoxy resin and epoxy curing agent, organic fluorine, polyaniline/carbon nano-fiber composite material,
Organic solvent；The top layer component is organic fluorine, Nano filling, silicon fluoride coupling agent, the You Jirong of low-surface-energy modification
Agent；The epoxy resin, epoxy curing agent, organic fluorine, polyaniline/carbon nano-fiber composite material, organic solvent
Mass ratio be 1：(0.1~0.2)：(0.1~0.3)：(0.05~0.15)：(10~15)；The organic fluorine, low table
Nano filling that face can be modified, silicon fluoride coupling agent, the mass ratio of organic solvent are 1：(0.1~0.2)：(0.05~0.15)：
(15~20)；
The polyaniline/carbon nano-fiber composite material preparation method is as follows：
（1）Carbon nano-fiber is modified：Carbon nano-fiber ultrasonic disperse is in nitration mixture, and the concentration of carbon nano-fiber is 1~5mg/mL,
It is heated to 80 DEG C and constant temperature and stirs 4 h, then be washed to distillation neutrality, dries 24 h under the conditions of 60 DEG C in an oven, obtain
The carbon nano-fiber of carboxylated；
（2）By the carbon nano-fiber ultrasonic disperse of carboxylated in 0.1~1 mol/L inorganic acid, sequentially add aniline monomer,
After ammonium persulfate oxidizing agent, the min of ultrasonic disperse 30, chemical oxidising polymerisation 24 h of reaction are carried out under the conditions of 0~4 DEG C, are obtained
Polyaniline/carbon nano-fiber composite material, is successively washed till neutrality with distilled water and ethanol, dries in an oven under the conditions of 60 DEG C
24 h。
2. the conductive multifunctional anticorrosive coating of a kind of high performance super-amphiphobic according to claim 1, it is characterised in that：It is described
Bottom component and top layer constituent mass ratio are 1：(1~2).
3. the conductive multifunctional anticorrosive coating of a kind of high performance super-amphiphobic according to claim 1, it is characterised in that：
Described epoxy resin is glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidol amine ring
One kind in oxygen tree fat, linear aliphatic same clan epoxy resin and alicyclic based epoxy resin, its molecular weight is 1000~100000；
Described epoxy curing agent be triethylamine, tetrabutyl ammonium fluoride, diethylenetriamines, diisopropyl ethyl amine, N,
N- dimethylanilines, octadecyldimethyl tertiary amine, diaminodiphenylsulfone, methyl hexahydrophthalic anhydride, oleyl dimethyl tertiary amine, ten
At least one of two tertiary amines, benzyltriethylammoinium chloride, triethanolamine and imidazoles；
Described organic fluorine be polytetrafluoroethylene (PTFE), polytrifluorochloroethylene, Kynoar, ethylene-tetrafluoroethylene copolymer,
At least one of ethylene-chlorotrifluoro-ethylene copolymer, fluorinated ethylene propylene copolymer；
Described organic solvent is one kind in ethyl acetate, toluene, dimethylformamide.
4. the conductive multifunctional anticorrosive coating of a kind of high performance super-amphiphobic according to claim 1, it is characterised in that：It is described
Step（1）Middle nitration mixture is concentrated nitric acid and the concentrated sulfuric acid, and the concentrated nitric acid is 1 with concentrated sulfuric acid volume ratio：3；The step（2）In it is inorganic
Acid is one kind in phosphoric acid, sulfuric acid.
5. the conductive multifunctional anticorrosive coating of a kind of high performance super-amphiphobic according to claim 1, it is characterised in that：It is described
The initial reactive concentration of aniline is 0.93~4.65 g/L, and the carbon of the aniline monomer, ammonium persulfate oxidizing agent and carboxylated is received
The mass ratio of rice fiber is 1：2.5：(0.1~0.4).
6. the conductive multifunctional anticorrosive coating of a kind of high performance super-amphiphobic according to claim 1, it is characterised in that：It is described
The preparation method for the Nano filling that low-surface-energy is modified is as follows：
（1）Mixed liquor is made in ethanol, water and low-surface-energy modifying agent, volume ratio is 18：1：1, it is heated to 50 DEG C and constant temperature is stirred
Mix 30 min；
（2）Nano filling is added in above-mentioned mixed liquor, the wherein addition of Nano filling is 1~5mg/mL, in 50 DEG C of conditions
Lower constant temperature stirs 24 h, then with distillation water filtration, dries 24 h under the conditions of 60 DEG C in an oven, low-surface-energy is made and is modified
Nano filling.
7. the conductive multifunctional anticorrosive coating of a kind of high performance super-amphiphobic according to claim 6, it is characterised in that：It is described
Nano filling is at least one in nano silicon, molybdenum disulfide, carborundum, graphene, CNT, carbon nano-fiber
Kind；The particle diameter of the Nano filling is between 20~500 nm；Low-surface-energy modifying agent is gamma-aminopropyl-triethoxy-silane.
8. a kind of preparation method of the conductive multifunctional anticorrosive coating of high performance super-amphiphobic according to claim 1, including
Following steps：
（1）Metal base surface is pre-processed
Sandblasting or shot-peening, polishing, cleaning and drying and processing are carried out to metal base surface；
（2）The preparation of coating bottom strata
Subbing is configured, by epoxy resin, epoxy curing agent dissolving in organic solvent, stirs and cures
30 min, sequentially add organic fluorine and polyaniline/carbon nano-fiber composite material, the min of ultrasonic disperse 20, and magnetic force
20~30 min are stirred, that is, subbing is made；
In step（1）Sprayed layer undercoat coating on metallic matrix after processing, by the metallic matrix after spraying with 2~6 DEG C/min's
Heating rate is warming up to 80~100 DEG C, and 1~2 h of solidification at a temperature of 80~100 DEG C；
（3）The preparation on coating top layer：
Successively by organic fluorine and the Nano filling of low-surface-energy modification, silicon fluoride coupling agent ultrasonic disperse in organic solvent
In, the min of magnetic agitation 20~30, then in above-mentioned steps（2）Continue to spray surface coating material on the bottom of preparation, after spraying
Metallic matrix be warming up to 200~300 DEG C with 2~6 DEG C/min heating rate, and solidify 1 at a temperature of 200~300 DEG C
~2 h, are down to after room temperature and obtain the conductive multifunctional anticorrosive coating of super-amphiphobic naturally.
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