CN105238207A - High performance super-amphiphobic conductive multi-functional corrosion-resistant coating and preparation method thereof - Google Patents
High performance super-amphiphobic conductive multi-functional corrosion-resistant coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high performance super-amphiphobic conductive multi-functional corrosion-resistant coating, which is characterized by comprising a bottom layer component and a surface layer component, wherein the bottom layer component is epoxy resins, epoxy curing agents, organic fluorines, polyaniline/carbon nanofibers composite materials, the surface layer component is organic fluorines, low surface energy modified nanofillers and fluorine silane coupling agents. The high performance super-amphiphobic conductive multi-functional corrosion-resistant coating can have the advantages of superamphiphobic, drag reduction, abrasion resistance and pit corrosion resistance, and is low in cost. The invention further provides a method for preparing the high performance super-amphiphobic conductive multi-functional corrosion-resistant coating.
Description
Technical field
The present invention relates to and superly twoly dredge electric multifunctional anticorrosive coating preparation field, particularly a kind of have coating of super-hydrophobic, super oleophobic, drag-reducing abrasion-resisting and excellent pitting corrosion resistance and preparation method thereof in petroleum chemical industry.
Background technology
Corrosion is that the perforation of the puzzlement a great problem, particularly oil pipeline of petroleum chemical industry and storage tank is leaked and not only can be had a strong impact on oil field and normally produce, and causes huge financial loss and security incident, and also can produce serious consequence to society and environment.The preservative mechanism of traditional insulation organic coating is shielding effect, once coating exist pin hole or breakage, will form the corrosion cell of large negative electrode primary anode, make corrosion concentrate on pin hole or breakage, accelerates the pitting speed of pipeline.
Conductive coating constructed by organic polymer conductive polymer polyanaline (PANI) due to the passivation of metallic surface and electric field action, has resistance to pitting that insulating coating hardly matches, scratch resistance capability.Chinese patent CN102702920B(Waterborne Polyaniline Corrosion Protection Coatings and preparation method thereof), CN102702815B(UV Curing Anti-Corrosive Coatings), CN102702467B(waterborne polyurethane resin, Waterborne Polyaniline Corrosion Protection Coatings and preparation method thereof), the preparation method of the polyaniline-modified mesopore molecular sieve protective system of CN102643592B(), CN102108241B(phosphate doped polyaniline anticorrosive paint and preparation method thereof) all p-poly-phenyl amine corrosion protection coating carried out effective trial.
But still there are two key issues in layer/polyaniline conductive coating in practical engineering application, serious its large-scale promotion of restriction and development.(1) wear resistance of simple polyaniline coating, with the sticking power of metal base and the demand performances such as the drag reduction scale inhibition of fluid still not being reached to industrial application, especially traditional blended coated polyurethane, epoxy resin etc. are when being applied to oil mixing with water fluid line and equipment, and the wetting ability of coating can not meet the long-lasting protection demand of its drag-reducing abrasion-resisting scale inhibition; (2) polyaniline is a kind of macromole with the large π key of conjugation of very strong interaction, rigidity is large, and interchain hydrogen bond interacts strong, poorly soluble, classical chemistry or the PANI of electrochemical synthesis are amorphous powder, have a strong impact on its dispersing uniformity in the coating and processing characteristics.
Bionic super-hydrophobic surpasses oleophobic (super two thin) surface and can effectively suppress corrosives to the diffusion of coat inside, greatly improves the resistance to corrosion of coating, has broad application prospects.The present invention proposes super two open coat to be coupled with layer/polyaniline conductive coating first, and is constructed the corrosion protection coating that simultaneously can realize super-hydrophobic, super oleophobic, resistance to pitting by simple process, has great industrial application value.
It is low still to there is sticking power in existing super two open coat, wear no resistance, complicated process of preparation, the problems such as expensive raw material price, such as Chinese patent CN103408707A proposes the super two open coat of amphiphilic crosslinkable fluorine silicon resin, wherein coating material amphipathic crosslinkable fluorine silicon resin needs hydrogeneous organosilicon, containing epoxy, fluorine-containing material, improved silica and hydroaropic substance are mixed in solvent, join in reactor, and pass into rare gas element, stir under 60 ~ 140 DEG C of conditions, add catalyzer again, keep stirring 5 ~ 24h, again above-mentioned reactant is deposited in normal hexane or methyl alcohol and obtains.The preparation technology related to is loaded down with trivial details, severe reaction conditions; Chinese patent CN103881532A proposes the mixture of primary coat epoxy resin and solidifying agent, and face is coated with modification nano-silver thread solution, prepares super-double-hydrophobic surface.But nano-silver thread cost is higher, complicated process of preparation, surface layer wears no resistance.
Summary of the invention
The invention reside in the shortcoming and defect overcoming existing super two open coat and the layer/polyaniline conductive coating existed in background technology, and provide
onekind high performance superly twoly dredge electric multifunctional anticorrosive coating.This is high performance superly twoly dredges electric multifunctional anticorrosive coating, can possess simultaneously superly twoly to dredge, drag-reducing abrasion-resisting, resistance to pitting feature, with low cost.Present invention also offers a kind of high performance super two preparation method and application thereof of dredging electric multifunctional anticorrosive coating.
The present invention solves its problem and reaches by following technical scheme: this is high performance superly twoly dredges electric multifunctional anticorrosive coating, comprise bottom and two, top layer component, described bottom component is epoxy resin and epoxy curing agent, organic fluorine, polyaniline/carbon nano-fiber composite material, silicon fluoride coupling agent; Described top layer component is organic fluorine, the Nano filling of low surface energy modification, silicon fluoride coupling agent, organic solvent.
Described bottom component and top layer constituent mass are than being 1:(1 ~ 2); The mass ratio of described bottom epoxy resin, epoxy curing agent, organic fluorine, polyaniline/carbon nano-fiber composite material, organic solvent is 1:(0.1 ~ 0.2): (0.1 ~ 0.3): (0.05 ~ 0.15): (10 ~ 15); The mass ratio of the Nano filling of organic fluorine, low surface energy modification in described top layer, silicon fluoride coupling agent, organic solvent is 1:(0.1 ~ 0.2): (0.05 ~ 0.15): (15 ~ 20).
Another object of the present invention is to provide a kind of super two preparation methods dredging electrocoat based on above-mentioned performance, comprises the steps:
(1) metal base surface pre-treatment
Sandblasting or shot-peening, polishing, cleaning and drying and processing are carried out to metal base surface;
(2) preparation of coating bottom
Configuration priming paint, dissolves epoxy resin, epoxy curing agent in organic solvent, stirs and slaking 30min, add organic fluorine and polyaniline/carbon nano-fiber composite material more successively, ultrasonic disperse 20min, and magnetic agitation 20 ~ 30min, i.e. obtained priming paint;
Sprayed layer undercoat coating on metallic matrix after step (1) process, is warming up to 80 ~ 100 DEG C by the metallic matrix after spraying with the temperature rise rate of 2 ~ 6 DEG C/min, and solidifies 1 ~ 2h at 80 ~ 100 DEG C of temperature;
(3) preparation on coating top layer:
Successively by the Nano filling of organic fluorine and low surface energy modification, silicon fluoride coupling agent ultrasonic disperse in organic solvent, magnetic agitation 20 ~ 30min, then the bottom prepared in above-mentioned steps (2) continues spraying surface coating material, metallic matrix after spraying is warming up to 200 ~ 300 DEG C with the temperature rise rate of 2 ~ 6 DEG C/min, and 1 ~ 2h is solidified at 200 ~ 300 DEG C of temperature, obtain after being naturally down to room temperature and wholely superly twoly dredge electrocoat.
The high performance super two principle of dredging electric multifunctional anticorrosive coating technology scheme of the present invention:
1. polyaniline/carbon nano-fiber composite material
The mechanism that employing in-situ chemical polymerization prepares polyaniline/carbon nano-fiber composite material is as follows: the carboxylated process of carbon nanofiber is easily in aqueous dispersed afterwards, first the aniline monomer be dissolved in water is adsorbed on carbon nanofiber surface, then issue biochemical oxidative polymerization in the initiation of oxygenant and mineral acid, form the electrically conductive polyaniline of doping state.In the polymerization process of aniline, carbon nanofiber plays skeletal support effect, aniline is slowly polymerized for riding in around it with carbon nanofiber, and polyaniline molecule and carbon nanofiber are interacted by electrostatic interaction and π-π and combine closely, and finally form polyaniline/carbon nano-fiber composite material.
The pi-pi accumulation structure existed between quinone ring structure on carbon nanofiber and polyaniline backbone, can stablize the quinoid structure of polyaniline, strengthens the reversible electroconductibility of polyaniline.And carbon nanofiber and polyaniline composite material can form network structure, good with organic consistency, greatly can improve conductivity and the mechanical property of coating.
2. the reaction mechanism of Nano filling
The low surface energy properties-correcting agent of described Nano filling is γ-aminopropyl triethoxysilane, amino and the oxyethyl group containing two kinds of different active groups, be used for coupling organic polymer and mineral filler, filler wettability in the polymer and dispersiveness can be improved, strengthen interface adhesion.The reaction mechanism of modification comprises: the ethoxy hydrolysis that (1) is connected with Siliciumatom, generation-Si-OH; (2) dehydrating condensation between-Si-OH, generates the oligosiloxane containing-Si-OH; (3)-the Si-OH in oligosiloxane forms hydrogen bond with the hydroxyl-OH of inorganic filler surface; (4) in heat curing process, form covalent linkage with dehydration reaction with organic epoxy resin and be connected, thus improve the water ratio limit intensity of matrix material.
3. super-double-hydrophobic surface formation mechenism
Adopt the Nano filling of low surface energy modification to be dispersed in organic fluorine, reduce the capillary Nano/micron of structure simultaneously binary coarse structure at coatingsurface, form the top layer of ultra-amphosphobic energy.
4. the Wear Resistance Mechanism of coating
The Nano filling of low surface energy modification is dispersed in organic fluorine coat inside and can plays the wear-resisting effect of enhancing coating, and mechanism of action is: 1. Nano filling produces stress concentration effect in friction process, plays coating toughening effect; 2. Nano filling can not produce large extension strain under action of pulling stress, can make coating crack passivation; 3. the specific surface area of Nano filling is large, the physics and chemistry defect on surface is a lot, therefore Nano filling and organic fluorine contact area are large and combined closely by physics and chemistry effect, can impact energy in absorber coatings friction process, avoid coating cracking, ensure the long-acting wear resistant ultra-amphosphobic energy of coating.
The present invention uses the epoxy resin of sticking power excellence and the organic fluorine of low surface energy to be coated substrate, adopts the high-pressure air spraying coating process being simple and easy to mass-producing to prepare and superly twoly dredges electric compound coating.In addition, carbon nanofiber has unique structure, very high length-to-diameter ratio, higher effective ratio area, good conduction, heat conduction and mechanical property, can strengthen mechanics and the conductivity of polyaniline high molecular polymer.Prepared polyaniline/carbon nano-fiber composite material combines the advantage of conducting polymer and nano material, has the Wuli-Shili-Renli system approach not available for many macroscopic material, as dimensional effect, quantum effect, surface effects.Therefore, the present invention prepares polyaniline/carbon nano-fiber composite material as coated conductive filler, in super two open coat matrix, build conductive network, can realize excellent antiseptic property.
The present invention can have following beneficial effect compared with above-mentioned background technology: this is high performance superly twoly dredges electric multifunctional anticorrosive coating, bottom strong adhesion, resistance to pitting; Super two thin, the wear-resisting drag reduction of surface layer; Bottom adds a small amount of organic fluorine, can with the organic fluorine crosslinking curing on top layer, ensure the cohesive strength of interlayer and consistency; The preparation technology that the present invention adopts is simple, low in raw material price, easy industrialization large-scale application.
Accompanying drawing explanation
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 transmission electron microscope pictures of polyaniline/carbon nano-fiber composite material in inventive embodiments 1;
Accompanying drawing 3 is super two surface topography maps dredging electrocoat in inventive embodiments 1;
Accompanying drawing 4 superly in inventive embodiments 1 twoly dredges the contact angle figure of electrocoat to water;
Accompanying drawing 5 superly in inventive embodiments 1 twoly dredges the contact angle figure of electrocoat to ethylene glycol;
Accompanying drawing 6 superly in inventive embodiments 1 twoly dredges the contact angle figure of electrocoat to glycerine;
Accompanying drawing 7 superly in inventive embodiments 1 twoly dredges the contact angle figure of electrocoat to crude oil;
Accompanying drawing 8 superly in inventive embodiments 1 twoly dredges the dynamic potential polarization curve of electrocoat in 3.5wt%NaCl etchant solution;
Accompanying drawing 9 is pure aluminum plate impedance charts in 3.5wt%NaCl etchant solution in inventive embodiments 1;
Accompanying drawing 10 superly in inventive embodiments 1 twoly dredges the impedance chart of electrocoat in 3.5wt%NaCl etchant solution.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1:
Take nano silicon as Nano filling, with epoxy resin, ethylene-tetrafluoroethylene copolymer, fluorinated ethylene propylene copolymer for coated substrate, on aluminium sheet, preparation has the super two of excellent antiseptic property and dredges electrocoat, and detects the antiseptic property of coating in strong acid, highly basic and high salt concentration water surrounding.
(1) carbon nanofiber modification
After 30mL concentrated nitric acid and the 90mL vitriol oil mix, add 0.5g carbon nanofiber, be heated to 80 DEG C by constant temperature blender with magnetic force and constant temperature stirring 4h, after being cooled to room temperature, be washed till neutrality with distilled water, finally dry 24h under 60 DEG C of conditions in an oven, obtain carboxylated carbon nanofiber.
(2) preparation of polyaniline/carbon nano-fiber composite material
Preparation 1L concentration is the sulphuric acid soln of 0.2mol/L, gets the carboxylated carbon nanofiber of 0.1g and is added in 500mL sulphuric acid soln (0.2mol/L), ultrasonic disperse 30min; Add in 1g aniline monomer to above-mentioned solution, ultrasonic agitation 12h; Getting 2.5g ammonium persulphate is dissolved in 500mL sulphuric acid soln (0.2mol/L), with aniline/carbon nanofiber solution short mix, under 0 ~ 4 DEG C of condition, chemical oxidising polymerisation reaction 24h is carried out after ultrasonic disperse 30min, then the throw out distilled water of generation and ethanol suction filtration are washed till neutrality, dry 24h under 60 DEG C of conditions, obtains blackish green polyaniline/carbon nano-fiber composite material in an oven.
(3) preparation of the Nano filling of low surface energy modification
Add ethanol 36mL, water 2mL successively, γ-aminopropyl triethoxysilane 2mL makes mixed solution, be heated to 50 DEG C by constant temperature blender with magnetic force and constant temperature stirs 30min; In above-mentioned mixed solution, add 0.2g nano silicon (particle diameter is about 50nm), under 50 DEG C of conditions, constant temperature stirs 24h; Modified inorganic nano-filler distilled water is filtered cleaning, finally dry 24h under 60 DEG C of conditions in an oven.
(4) coating preparation
The pre-treatment of metal base: using area be the aluminium sheet of 8cm × 8cm as substrate, establishing criteria " before application steel surface rusty degree and derusting grade " (GB8923-88), polishes to St3 grade standard step by step with 360 orders, 600 orders and 1000 order sand paper respectively.To polish rear deionized water rinsing, clean oil removing with acetone and dry;
The preparation of coating bottom: with the area of one side coating, get 1g bisphenol A type epoxy resin (E-44), the many amine curing agents of 0.2g dissolve in organic solvent, stir and slaking 30min, then 0.2g ethylene-tetrafluoroethylene copolymer and polyaniline/carbon nano-fiber composite material is added successively, ultrasonic disperse 20min, and magnetic agitation 20 ~ 30min; The priming paint of preparation is sprayed into pretreated substrate surface, and spray distance is 12 ~ 15cm, and air pressure is 0.5bar, is warming up to 80 DEG C with the temperature rise rate of 2 ~ 6 DEG C/min, under 80 DEG C of conditions, solidify 1h;
The preparation on coating top layer: get 1g ethylene-tetrafluoroethylene copolymer, 0.5g fluorinated ethylene propylene copolymer, the nano silicon of 0.15g low surface energy modification and 0.1g silicon fluoride coupling agent ultrasonic disperse in 20mL ethyl acetate, spray as surface coating material after magnetic agitation 30min, spray distance is 12 ~ 15cm, air pressure is 0.5bar, finally be warming up to 300 DEG C with the temperature rise rate of 2 ~ 6 DEG C/min in an oven, and 2h is solidified under 300 DEG C of conditions, obtain super two thin top layer after being naturally down to room temperature.
(5) performance test and effect
Coating morphology and composition test and result: adopt scanning electronic microscope and transmission electron microscope observing to find, polyaniline realizes growth in situ on carbon nanofiber surface, polyaniline/carbon nano-fiber composite material is intersection network fibres structure, as shown in accompanying drawing 1 and Fig. 2; The specific conductivity of polyaniline/carbon nano-fiber composite material is 3.5S/cm; Prepared super two electrocoat surfaces of dredging are Nano/micron diadactic structure, as shown in Figure 3;
Ultra-amphosphobic can be tested and result: adopt Static Contact angle measuring instrument to measure the contact angle of coating to water, ethylene glycol, glycerine and crude oil and be respectively 168 °, 159 °, 156 ° and 155 °, it is 5 ° to the roll angle of oil-water mixture (crude oil and water volume ratio are 1:9), as shown in accompanying drawing 4, Fig. 5, Fig. 6, Fig. 7, therefore this coating can realize super-hydrophobic, super oleophobic, the attachment of coatingsurface pollutent is reduced for oil-water mixture fluid line, realizes drag-reducing abrasion-resisting and there is unique advantage.
Sticking power test and result: according to standard GB/T/T9286-1998 " cross cut test of paint and varnish paint film ", ground is penetrated into cartesian mesh pattern cut coating, coating cut edge prepared by this example is completely level and smooth, none lattice comes off, and therefore this coating has reached best adhesion effect 0 grade.
Wearability test and result: prepared coating is rubbed repeatedly with 1000 order sand paper, test pressure is 10N, after 10000 frictions, coating does not gall, and coating hydrophobic angle still remains on 158 °, remaining on 152 and 151 ° to the contact angle of glycerine and crude oil, is 9 ° to the roll angle of oil-water mixture (crude oil and water volume ratio are 9:1), explanation coating wear resistance is excellent, and still can keep ultra-amphosphobic energy after long-time friction.
Acid-alkali-corrosive-resisting test and result: prepared super two open coat to be soaked in strong acid (pH=1) and highly basic (pH=14) solution 30 days, adopt scanning electronic microscope (SEM) to observe apparent form, find that coating still can keep receiving micro-diadactic structure roughness; The hydrophobic angle of the coating after soaking in strong acid and highly basic is respectively 153 ° and 151 °, 149 ° and 145 ° are respectively to the contact angle of crude oil, show that coating still can keep well super-hydrophobic and oleophobic performance, this coating can be applied in actual corrosive environment.
Galvanic corrosion protection test and result: super two electrocoat of dredging will be scribbled and to be soaked in 3.5%NaCl corrosive medium 120 days, and measure its open circuit potential, ac impedance spectroscopy and dynamic potential polarization curve.Being to electrode with platinum plate electrode, take saturated calomel electrode as reference electrode, and test is carried out at ambient temperature.As shown in Figure 8, result shows that coating is at immersion 120 days post-etching electromotive force (E to dynamic potential polarization curve figure
corr) to have shuffled 358mV than pure aluminum plate, corrosion current to decline about 3 orders of magnitude than pure aluminum plate, and corrosion prevention efficiency is up to being 99.9%; Pitting is there is in ac impedance spectroscopy (see accompanying drawing 9, Figure 10) result display pure aluminum plate after immersion 30min, and super two aluminium sheet dredging electrocoat protection still keeps excellent antiseptic property in immersion after 120 days, illustrate that this coating has excellent long-effective corrosion ability to aluminium sheet.
Embodiment 2:
Take nano molybdenum disulfide as filler, with epoxy resin, poly-inclined tetrafluoroethylene, fluorinated ethylene propylene copolymer for coated substrate, on steel plate, preparation is super twoly dredges electric protection coating.
Prepare according to the step of embodiment 1, be with the difference of embodiment 1:
In step (1), the concentration of carbon nanofiber in mixed acid solution is 3mg/mL;
In step (2), the mass ratio of aniline and carboxylated carbon nanofiber is 1:0.2;
In step (3), Nano filling adopts nano molybdenum disulfide, and particle diameter is about 80nm, and working concentration is 3mg/mL;
The steel plate of sheet material X80 material commonly used by step (4) floating coat choice of the substrates petroleum pipe line; The mass ratio of priming paint neutral line aliphatic category epoxy resin, polyamide-based solidifying agent, poly-inclined tetrafluoroethylene, polyaniline/carbon nano-fiber composite material, ethyl acetate solvent is 1:0.15:0.2:0.1:15; Investment precoat select polyvinylidene difluoride (PVDF), fluorinated ethylene propylene copolymer, the nano molybdenum disulfide of low surface energy modification, silicon fluoride coupling agent, ethyl acetate solvent mass ratio be 1:0.3:0.15:0.1:20;
Step (5) floating coat the performance test results is: the specific conductivity of polyaniline/carbon nano-fiber composite material is 3.8S/cm; The contact angle of coating to water, ethylene glycol, glycerine and crude oil is respectively 169 °, 158 °, 157 ° and 154 °, is 4 °, illustrates that this coating can realize super-hydrophobic, super oleophobic to the roll angle of oil-water mixture (crude oil and water volume ratio are 1:9); Sticking power test result shows that coating adhesion effect belongs to best adhesion effect 0 grade; Frictional experiment result is coating hydrophobic angle after 10000 frictions is 157 °, it is 153 ° and 151 ° to the contact angle of glycerine and crude oil, it is 8 ° to the roll angle of oil-water mixture (crude oil and water volume ratio are 1:9), explanation coating wear resistance is excellent, and can keep ultra-amphosphobic energy after friction for a long time; Coating is soaked after 90 days in strong acid (pH=1) and highly basic (pH=14), and hydrophobic angle is 154 ° and 152 °, is respectively 150 ° and 148 ° to the contact angle of crude oil, shows that coating has stable super-hydrophobic and oleophobic performance in actual corrosive environment; Electrochemical anti-corrosive the performance test results shows, the coating open circuit potential that soaks coating after 120 days in 3.5%NaCl corrosive medium have been shuffled 375mV than clean steel plate, corrosion prevention speed is 99.9%, ac impedance spectroscopy display etchant solution does not enter coat inside, illustrates that this coating has excellent long-lasting protection ability to base material.
Claims (10)
1. high performancely superly twoly dredge electric multifunctional anticorrosive coating for one kind, it is characterized in that: comprise bottom and two, top layer component, described bottom component is epoxy resin and epoxy curing agent, organic fluorine, polyaniline/carbon nano-fiber composite material, organic solvent; Described top layer component is organic fluorine, the Nano filling of low surface energy modification, silicon fluoride coupling agent, organic solvent.
2. one according to claim 1 is high performance superly twoly dredges electric multifunctional anticorrosive coating, it is characterized in that: described bottom component and top layer constituent mass are than being 1:(1 ~ 2).
3. one according to claim 1 is high performance superly twoly dredges electric multifunctional anticorrosive coating, it is characterized in that: the mass ratio of described epoxy resin, epoxy curing agent, organic fluorine, polyaniline/carbon nano-fiber composite material, organic solvent is 1:(0.1 ~ 0.2): (0.1 ~ 0.3): (0.05 ~ 0.15): (10 ~ 15); The mass ratio of the Nano filling of described organic fluorine, low surface energy modification, silicon fluoride coupling agent, organic solvent is 1:(0.1 ~ 0.2): (0.05 ~ 0.15): (15 ~ 20).
4. one according to claim 1 is high performance superly twoly dredges electric multifunctional anticorrosive coating, it is characterized in that:
Described epoxy resin is the one in glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic same clan epoxy resin and alicyclic based epoxy resin, and its molecular weight is 1000 ~ 100000;
Described epoxy curing agent is at least one in triethylamine, tetrabutyl ammonium fluoride, diethylenetriamine, diisopropyl ethyl amine, DMA, octadecyldimethyl tertiary amine, diaminodiphenylsulfone(DDS), methyl hexahydrophthalic anhydride, oleyl dimethyl tertiary amine, dodeca-tertiary amine, benzyltriethylammoinium chloride, trolamine and imidazoles;
Described organic fluorine is at least one in tetrafluoroethylene, voltalef, polyvinylidene difluoride (PVDF), ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer, fluorinated ethylene propylene copolymer, fluorinated ethylene propylene;
Described organic solvent is the one in ethyl acetate, toluene, dimethyl formamide.
5. one according to claim 1 is high performance superly twoly dredges electric multifunctional anticorrosive coating, it is characterized in that: described polyaniline/carbon nano-fiber composite material preparation method is as follows:
(1) carbon nanofiber modification: carbon nanofiber ultrasonic disperse is in nitration mixture, the concentration of carbon nanofiber is 1 ~ 5mg/mL, is heated to 80 DEG C and constant temperature stirring 4h, then is washed till neutrality with distilled water, dry 24h under 60 DEG C of conditions, obtains carboxylated carbon nanofiber in an oven;
(2) by carboxylated carbon nanofiber ultrasonic disperse in the mineral acid of 0.1 ~ 1mol/L, add aniline monomer, ammonium persulfate oxidizing agent successively, after ultrasonic disperse 30min, chemical oxidising polymerisation reaction 24h is carried out under 0 ~ 4 DEG C of condition, obtain polyaniline/carbon nano-fiber composite material, priority distilled water and ethanol are washed till neutrality, in an oven dry 24h under 60 DEG C of conditions.
6. one according to claim 5 is high performance superly twoly dredges electric multifunctional anticorrosive coating, it is characterized in that: in described step (1), nitration mixture is concentrated nitric acid and the vitriol oil, and described concentrated nitric acid and vitriol oil volume ratio are 1:3; In described step (2), mineral acid is the one in phosphoric acid, sulfuric acid.
7. one according to claim 5 is high performance superly twoly dredges electric multifunctional anticorrosive coating, it is characterized in that: the initial reactive concentration of described aniline is 0.93 ~ 4.65g/L, the mass ratio of described aniline monomer, ammonium persulfate oxidizing agent and carboxylated carbon nanofiber is 1:2.5:(0.1 ~ 0.4).
8. one according to claim 1 is high performance superly twoly dredges electric multifunctional anticorrosive coating, it is characterized in that: the preparation method of the Nano filling of described low surface energy modification is as follows:
(1) ethanol, water and low surface energy properties-correcting agent are made mixed solution, volume ratio is 18:1:1, is heated to 50 DEG C and constant temperature stirring 30min;
(2) in above-mentioned mixed solution, add Nano filling, wherein the add-on of Nano filling is 1 ~ 5mg/mL, and under 50 DEG C of conditions, constant temperature stirs 24h, then filters with distilled water, dry 24h under 60 DEG C of conditions in an oven, the Nano filling of obtained low surface energy modification.
9. one according to claim 8 is high performance superly twoly dredges electric multifunctional anticorrosive coating, it is characterized in that: described Nano filling is at least one in nano silicon, molybdenumdisulphide, silicon carbide, Graphene, carbon nanotube, carbon nanofiber; The particle diameter of described Nano filling is between 20 ~ 500nm; Low surface energy properties-correcting agent is γ-aminopropyl triethoxysilane.
10. the high performance super two preparation method dredging electric multifunctional anticorrosive coating according to claim 1, comprises the steps:
(1) metal base surface pre-treatment
Sandblasting or shot-peening, polishing, cleaning and drying and processing are carried out to metal base surface;
(2) preparation of coating bottom
Configuration priming paint, dissolves epoxy resin, epoxy curing agent in organic solvent, stirs and slaking 30min, add organic fluorine and polyaniline/carbon nano-fiber composite material more successively, ultrasonic disperse 20min, and magnetic agitation 20 ~ 30min, i.e. obtained priming paint;
Sprayed layer undercoat coating on metallic matrix after step (1) process, is warming up to 80 ~ 100 DEG C by the metallic matrix after spraying with the temperature rise rate of 2 ~ 6 DEG C/min, and solidifies 1 ~ 2h at 80 ~ 100 DEG C of temperature;
(3) preparation on coating top layer:
Successively by the Nano filling of organic fluorine and low surface energy modification, silicon fluoride coupling agent ultrasonic disperse in organic solvent, magnetic agitation 20 ~ 30min, then the bottom prepared in above-mentioned steps (2) continues spraying surface coating material, metallic matrix after spraying is warming up to 200 ~ 300 DEG C with the temperature rise rate of 2 ~ 6 DEG C/min, and 1 ~ 2h is solidified at 200 ~ 300 DEG C of temperature, obtain after being naturally down to room temperature and wholely superly twoly dredge electrocoat.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639278A (en) * | 2002-07-03 | 2005-07-13 | Ad技术株式会社 | Anti-corrosion paint for steel with polyaniline |
| CN101955631A (en) * | 2010-09-17 | 2011-01-26 | 中国民航大学 | Preparation method of polyaniline modified multi-wall carbon canotube/epoxy resin composite material |
| CN104201007A (en) * | 2014-08-29 | 2014-12-10 | 中科院广州化学有限公司 | Carbon nanomaterial-based flexible super capacitor electrode material and preparation method for same |
| CN104371498A (en) * | 2014-11-13 | 2015-02-25 | 东北石油大学 | Super-amphiphobic coating with persistent anticorrosion and abrasion resistances and preparation method of super-amphiphobic coating |
-
2015
- 2015-10-22 CN CN201510689709.1A patent/CN105238207B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639278A (en) * | 2002-07-03 | 2005-07-13 | Ad技术株式会社 | Anti-corrosion paint for steel with polyaniline |
| CN101955631A (en) * | 2010-09-17 | 2011-01-26 | 中国民航大学 | Preparation method of polyaniline modified multi-wall carbon canotube/epoxy resin composite material |
| CN104201007A (en) * | 2014-08-29 | 2014-12-10 | 中科院广州化学有限公司 | Carbon nanomaterial-based flexible super capacitor electrode material and preparation method for same |
| CN104371498A (en) * | 2014-11-13 | 2015-02-25 | 东北石油大学 | Super-amphiphobic coating with persistent anticorrosion and abrasion resistances and preparation method of super-amphiphobic coating |
Non-Patent Citations (1)
| Title |
|---|
| 王慧慧: "聚苯胺/碳纳米管复合导电防腐涂层的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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