CN102424739A - Heatproof anticorrosion coating with ion barrier ability and selectivity and preparation method thereof - Google Patents
Heatproof anticorrosion coating with ion barrier ability and selectivity and preparation method thereof Download PDFInfo
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- CN102424739A CN102424739A CN2011103633483A CN201110363348A CN102424739A CN 102424739 A CN102424739 A CN 102424739A CN 2011103633483 A CN2011103633483 A CN 2011103633483A CN 201110363348 A CN201110363348 A CN 201110363348A CN 102424739 A CN102424739 A CN 102424739A
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Abstract
The invention relates to a heatproof anticorrosion coating with the ion barrier ability and selectivity, a preparation method thereof, a purpose of the heatproof anticorrosion coating in metal materials, especially steel materials, and corresponding anticorrosion processing methods of the metal materials. The anticorrosion coating of the invention comprises an anionic selectivity layer and a cationic selectivity layer, wherein the anionic selectivity layer and the cationic selectivity layer are films comprising a matrix material and a layered inorganic material intercalation, the Zeta potential of the layered inorganic material is from -50mV to 50mV, and the matrix material is an anticorrosion polymer which is an epoxy resin, a phenolic resin, acrylic resin or a polyamide polymeric material. The anticorrosion coating of the invention, which can be applied to steel materials in a high chloride ion content corrosion environment, underground pipelines, sea platforms, seabed pipelines, steamships and the like, has a good anticorrosion performance.
Description
Technical field
The present invention relates to the rotproofing field; Be particularly related to be used to form and have ion barrier and heat-resistant anticorrosive coating and preparation method thereof optionally; Said corrosion protection coating can be used for metallic substance particularly in the heat-resistant anticorrosive of steel material, and the method for anticorrosion treatment of corresponding metal material.
Background technology
Metallic substance can receive the influence of surrounding environment inevitably in the process under arms and corrode.Prevent that the metallic material corrosion domestic method from having electro-chemical protection, coating or film protection and inhibiter protection etc.Wherein organic coating or film are anticorrosion because characteristics such as simple, easy construction become one of the most frequently used method of anti-corrosion of metal.Organic coating commonly used or film mainly are used for accomplishing through physical shielding to the Metal Protection effect.Because macromolecular material inherent characteristic, cause certainly existing textural defect such as some pores, tiny crack in organic coating or the film, pass the passage that coating or film enter into metal base surface thereby become corrosive medium easily, cause the corrosion of metallic matrix.Though can delay metal to a certain extent and corrode through in coating or film, adding anticorrosive packing, increase coating or film thickness or adjusting method such as construction technology, can not fundamentally solve the problem of metallic corrosion.
Later 1970s; N.Sato finds that the corrosion deposited film of resistant metal has ion selectivity; Deposited film has cation selective and anion-selective respectively towards the outer of environment with towards the internal layer of metal, is similar to semi-conductive P-N P-N junction characteristicPN, and this Bipolar Membrane has stoped the intrusion of extraneous ion such as cl ions outwardly; Inwardly stoped metallic cation to external migration; And promote to form fine and close anhydrous oxide internal layer, impel metal to produce passivation, to metal (the N.Sato.Toward a More Fundamental Understanding of Corrosion Processes.Corrosion that plays a protective role; 1989, Vol.45 (5): 354～368).Research has subsequently produced the Bipolar Membrane mechanism (Bipolar Mechanism of Passivity) of passivation.
People such as the Wang Zhoucheng of Xiamen University are according to above-mentioned metal passivation notion; Characteristic at principle and technical combination passive film and organic coating or film; The ion selectivity coating or the film that have prepared the dopant ion exchange resin are (referring to the corrosion electrochemistry behavior of .A3 steel such as Wang Zhoucheng under ion selectivity coating or film; " Xiamen University's journal (natural science edition) ", 1997,36 (1): 388-393; Wang Zhoucheng etc., different ions permutoid are to the influence of the corrosion behavior of carbon steel under organic coating or film, " material protection ", 2001,34 (10): 9-10; Wang Zhoucheng, ion selectivity phenolic coating or film be to the research of carbon steel antiseptic property, " material protection ", 1998,31 (3): 1-3).J.G Wang etc. discovers that the protonic acid doping polyaniline has the characteristics of anionresin (J.G.Wang; Anion exchange nature of emeraldine base (EB) polyaniline (PAn) and a revisit of the EB formula, Synth.Met.132 (2002) 49-52).The coating or the film of epoxy resin and polyaniline blend are made priming paint; The epoxy coating or the film that are mixed with Zeo-karb are done bipolarity coating or the film that finish paint obtains; Its antiseptic property is superior to single cation selective coating or film and anion-selective coating or film (J.G.Wang, Ch.C.Torardi, M.W.Duch; Polyaniline-related ion-barrier anticorrosion coatings I.Ionic permeability of polyaniline; Cationic, and bipolar films, Synth.Met.157 (2007) 846-850; J.G.Wang; Ch.C.Torardi; M.W.Duch, Polyaniline-related ion-barrier anticorrosion coatings II.Protection behavior of polyaniline, cationic; And bipolar films, Synth.Met.157 (2007) 851-854).But; What the charged particle in above-mentioned coating or the film adopted is micron-sized ion exchange resin; Volume is bigger, makes itself and matrix contact interface place be prone to defective, forms " pin hole "; Ion exchange resin has very strong water-absorbent simultaneously, and this is a fatal defective for coating or film.
CN101463200A joins nano_scale particle that itself has certain electric charge or the nanoparticle that has electric charge after treatment in the filmogen as filler, obtains having the bipolarity nano coating or the film of ion selectivity, has preservative effect preferably.This coating is to be used for realizing anti-corrosion function through what inside and outside two membranes had an ion selectivity.
Laminated inorganic matter is because it has unique laminate structure advantage, and the superior mechanical property, thermal property and the dimensional stability that reveal with the polymkeric substance composite table have received people's attention.Type according to laminated inorganic matter; Epoxy resin/laminated inorganic matter nano composite material has two big types: with polynite (MMT) be representative-epoxy resin/cationic laminated inorganic matter matrix material, be the epoxy resin/anion type laminated composite material of inorganic matter of representative with hydrotalcite (LDH).
Polynite is one type of natural layered silicate quasi-mineral, and main characteristic is that specific surface area is big, and moisture makes its expansion easily with other organic molecules, causes interlamellar spacing to increase.Polynite entire structure lamella comprises three subgrades, in the middle of two-layer silicon-oxy tetrahedron subgrade, is embedded an alumina octahedral subgrade, shared Sauerstoffatom between silicon-oxy tetrahedron and the alumina octahedral, the Al in the part lattice
3+By Mg
2+Or Si
4+By Al
3+Isomorphous substitution, thereby crystal layer is electronegative.Superfluous negative charge is by being free on the Na of interlayer
+, Ca
2+Keep charge balance, so sheet surfaces is adsorbed metallic cation easily.Polynite after the exchange is oleophilicity, and the distance between cheating engaging layer increases.
Consisting of of hydrotalcite: Mg
6Al
2(OH)
16CO
3.4H
2O.Mg
2+And Al
3+On its skeleton, occupy at OH in order
-In the closely packed octahedral site of ion, form the oxyhydroxide unit layer of two dimension with superfluous positive charge, this element layer is by the CO of bound water molecule
3 2-Sheath separates and reaches charge balance.Mg in skeleton
2+, Al
3+Respectively by other iso-valence metal cationic moieties or whole isomorphous substitution, or interlayer CO
3 2-All be called houghite by the hydrotalcite of other anionresins, chemical general formula is: [M
2+ 1-XM
3+ X(OH)
2]
X+[A
N- X/n.mH
2O].M in the formula
2+, M
3+Be respectively divalence and tervalent metallic cation, A is the negatively charged ion of different valence mumbers, and X is M
3+/ (M
2++ M
3+) the element mol ratio, m is an interlayer combined moisture subnumber.Hydrotalcite has characteristics such as interlayer anion interchangeability, skeleton positively charged ion isomorphous substitution property and thermal degradation, is a kind of multifunctional macromolecule material modification auxiliary agent.Similar with polynite, hydrotalcite also is a kind of two-dimensional layer material, and difference is that it is an anionic type laminated material, thus can change the interlayer structure of hydrotalcite through IX equally, thus carry out organically-modified.
Correlative study shows; MMT or LDH join the iris action that can significantly improve coating in the polymkeric substance, reduce the water-absorbent of coating, improve the preservative effect (M.R.Bagherzadeh of polymeric coating; F.Mahdavi; Preparation of epoxy-clay nanocomposite and investigation on its anti-corrosive behavior in epoxy coating.Prog.Org.Coat., 2007,60 (2): 117-120; Fazhi Zhang et al.Fabrication of oriented layered double hydroxide films by spin coating and their use in corrosion protection, Chemical Engineering Journal 141 (2008) 362-367; R.G.Buchheit, H.Guan.Active corrosion protection and corrosion sensing in chromate-free organic coatings, Prog.Org.Coat.2003,47 (6): 174-182; Sun Meng, the spin-coating method preparation of LDHs film and Corrosion Protection research thereof, Beijing University of Chemical Technology's master thesis, 2007).
But the preservative activity of above-mentioned related coatings has plenty of and utilizes ion selectivity to accomplish, and has plenty of that the iris action that utilizes filler accomplishes.The difference of the present invention and above-mentioned coating is that coatings prepared not only has ion selectivity but also have synusia shape iris action, so its preservative effect has had bigger raising to a certain extent.
Summary of the invention
The object of the present invention is to provide a kind of coating, it not only has ion selectivity, and owing to the synusia shape physics shape characteristic of filler, this coating also has the physical barrier effect for the infiltration of objectionable impurities simultaneously.
At first, the invention provides a kind of ion barrier and selectivity heat-resistant anticorrosive coating composition, said composition comprises:
Can form the positively charged synusia shape inorganic materials and the body material of interlayer of anion-selective layer; And
Can form the electronegative synusia shape inorganic materials and the body material of interlayer of cation selective layer.
Secondly, the present invention also provides a kind of ion barrier and selectivity heat-resistant anticorrosive coating, and this coating comprises:
The anion-selective layer, said anion-selective layer is formed by interlayer positively charged synusia shape inorganic materials and body material; And
The cation selective layer, said cation selective layer is formed by interlayer electronegative synusia shape inorganic materials and body material.
In a specific embodiments of the present invention, the electro kinetic potential (Zeta potential) of the synusia shape inorganic materials that said interlayer is positively charged is greater than 0 with smaller or equal to 50mV; The electro kinetic potential (Zeta potential) of the synusia shape inorganic materials that interlayer is electronegative is less than 0 with more than or equal to-50mV.
In a specific embodiments of the present invention, wherein, said body material is epoxy resin, resol, vinyl resin or polyamide polymers material.
In a specific embodiments of the present invention, wherein, the electronegative synusia shape inorganic materials of said interlayer is polynite or the polynite after modification is handled; The positively charged synusia shape inorganic materials of interlayer is hydrotalcite or the hydrotalcite after modification is handled.
In a specific embodiments of the present invention, wherein, the thickness of said anion-selective layer is 100～200 μ m, and the thickness of said cation selective layer is 100～200 μ m.
The present invention also provides a kind of method for preparing ion barrier and selectivity heat-resistant anticorrosive coating, and this method comprises:
Behind synusia shape inorganic materials intercalation first body material that interlayer is positively charged, mix with first solidifying agent, coating forms the anion-selective layer again; Then, behind synusia shape inorganic materials intercalation second body material that interlayer is electronegative, mix with second solidifying agent, coating forms the cation selective layer again, wherein coating cation selective layer on the anion-selective layer.
The present invention also provides the purposes of above-mentioned heat-resistant anticorrosive coating in metallic substance is anticorrosion.
The present invention also provides a kind of method for anticorrosion treatment of metallic substance, and this method comprises: form above-mentioned ion barrier and selectivity heat-resistant anticorrosive coating on the surface of metallic substance.
The present invention has used for reference the bipolarity theory of metal passivation, has prepared a kind of heat-resistant anticorrosive coating with ion iris action.Coating of the present invention can be used for especially steel material anticorrosion of metallic substance, is applicable to the anticorrosion of metallic substance in the high temperature Service Environment such as corrosive environment that chloride ion contents such as buried pipeline, ocean platform, submerged pipeline, steamer are higher and oil well pipe.Corrosion protection coating of the present invention has ion selectivity and iris action; For ion exchange resin Bipolar Membrane of the prior art, adopt synusia shape inorganic materials as charged particle among the present invention, can avoid occurring " pin hole " defective at prior art intermediate ion exchange resin Bipolar Membrane and basal body interface place; And corrosion protection coating of the present invention does not have the strong absorptive of ion exchange resin; Can further stop the infiltration of corrosive medium effectively, and, corrosion protection coating of the present invention; Preparation technology is easy, and application performance is good.
Description of drawings
Fig. 1 is the common ring oxygen coating soaks different time in 90 ℃ of 5% sodium chloride solution impedance-frequency plot;
Fig. 2 a is single cation selective coating is soaked different time in 90 ℃ of 5% sodium chloride solution impedance-frequency plot;
Fig. 2 b is single anion-selective coating is soaked different time in 90 ℃ of 5% sodium chloride solution impedance-frequency plot;
Fig. 3 is the coating in the embodiment of the invention 1 is soaked different time in 90 ℃ of 5% sodium chloride solution impedance-frequency plot;
Fig. 4 is the common ring oxygen coating soaks later stage and metallic contact interface in 90 ℃ of 5% sodium chloride solution microscopic appearance and energy spectrum analysis;
Fig. 5 is the coating in the embodiment of the invention 1 is soaked later stage and metallic contact interface in 90 ℃ of 5% sodium chloride solution microscopic appearance and energy spectrum analysis;
Fig. 6 is the anion-selective membrane for preparing behind the used synusia shape inorganic materials intercalation epoxy resin in the embodiment of the invention 1, the membrane potential figure of cation selective film;
Fig. 7 is the common ring oxygen coating soaks different time in 90 ℃ of 5% hydrochloric acid soln impedance-frequency plot;
Fig. 8 a is single cation selective coating is soaked different time in 90 ℃ of 5% hydrochloric acid soln impedance-frequency plot;
Fig. 8 b is single anion-selective coating is soaked different time in 90 ℃ of 5% hydrochloric acid soln impedance-frequency plot;
Fig. 9 is the coating in the embodiment of the invention 2 is soaked different time in 90 ℃ of 5% hydrochloric acid soln impedance-frequency plot;
Figure 10 a is that the epoxy resin varnish coating is simulated coating interface microscopic appearance and energy spectrum analysis behind the actual condition in high temperature and high pressure kettle;
Figure 10 b is that the cation selective coating is simulated coating interface microscopic appearance and energy spectrum analysis behind the actual condition in high temperature and high pressure kettle;
Figure 10 c is that the anion-selective coating is simulated coating interface microscopic appearance and energy spectrum analysis behind the actual condition in high temperature and high pressure kettle;
Figure 10 d is that the coating in the embodiment of the invention 3 is simulated coating interface microscopic appearance and energy spectrum analysis behind the actual condition in high temperature and high pressure kettle.
Embodiment
At first, the invention provides a kind of ion barrier and selectivity heat-resistant anticorrosive coating composition, said composition comprises:
Can form the positively charged synusia shape inorganic materials and the body material of interlayer of anion-selective layer; And
Can form the electronegative synusia shape inorganic materials and the body material of interlayer of cation selective layer.
Secondly, the present invention also provides a kind of ion barrier and selectivity heat-resistant anticorrosive coating, and this coating comprises:
The anion-selective layer, said anion-selective layer is formed by interlayer positively charged synusia shape inorganic materials and body material; And
The cation selective layer, said cation selective layer is formed by interlayer electronegative synusia shape inorganic materials and body material.
According to specific embodiments of the present invention, said body material can be the polymkeric substance with preservative activity, and wherein, said body material is epoxy resin, resol, vinyl resin or polyamide polymers material; The electronegative synusia shape inorganic materials of said interlayer is polynite or the polynite after modification is handled; The positively charged synusia shape inorganic materials of interlayer is hydrotalcite or the hydrotalcite after modification is handled.These inorganic layer flaky materials have nano level small size, do not absorb water through after the modification, have meliority than micron order ion exchange resin bead.
In a specific embodiments of the present invention; The rete that cation selective layer in the said heat-resistant anticorrosive coating with iris action forms for the montmorillonite intercalation handled through modification back in epoxy resin/resol, the rete that said anion-selective layer forms in epoxy resin/resol for the hydrotalcite intercalation handled through modification.
Among the present invention, said nano level typically refers to 0.1～100nm in said field.
According to specific embodiments of the present invention; Electro kinetic potential (the Zeta potential of said positively charged synusia shape material; The current potential that refers to shear surface; Be the important indicator that characterizes colloidal dispersion stability) greater than 0 with smaller or equal to 50mV, the Zeta potential of said electronegative synusia shape material is less than 0 with more than or equal to-50mV.
According to specific embodiments of the present invention; When heat-resistant anticorrosive coating of the present invention is used for the rotproofing of metallic substance; The thickness of said anion-selective layer is 100～200 μ m; The thickness of said cation selective layer is 100～200 μ m, and the thickness of Bulk coat can be controlled in 200～400 μ m usually, can reach good preservative effect.Usually, in the corrosive environment of O-level, the corrosion protection coating thickness of the regular grade that the present invention is prepared can be 200～300 μ m or littler, and wherein the thickness of individual layer yin, yang ion selective layer can be about 100 μ m or is littler; Compare in the serious environmental at extent of corrosion, corrosion protection coating of the present invention can be made into and add intensity level, adds intensity level corrosion protection coating integral thickness 300～400 μ m, wherein individual layer yin, yang ion selectivity layer thickness≤200 μ m.
The present invention also provides a kind of method for preparing ion barrier and selectivity heat-resistant anticorrosive coating, and this method comprises:
Behind synusia shape inorganic materials intercalation first body material that interlayer is positively charged, mix with first solidifying agent, coating forms the anion-selective layer again; Then, behind synusia shape inorganic materials intercalation second body material that interlayer is electronegative, mix with second solidifying agent, coating forms the cation selective layer again, wherein coating cation selective layer on the anion-selective layer.
The present invention also provides the purposes of above-mentioned heat-resistant anticorrosive coating in metallic substance is anticorrosion.
The present invention also provides a kind of method for anticorrosion treatment of metallic substance, and this method comprises: form above-mentioned ion barrier and selectivity heat-resistant anticorrosive coating on the surface of metallic substance.
Polynite is one type of natural layered silicate quasi-mineral, and main characteristic is that specific surface area is big, and moisture makes its expansion easily with other organic molecules, causes interlamellar spacing to increase.Polynite entire structure lamella comprises three subgrades, in the middle of two-layer silicon-oxy tetrahedron subgrade, is embedded an alumina octahedral subgrade, shared Sauerstoffatom between silicon-oxy tetrahedron and the alumina octahedral, the Al in the part lattice
3+By Mg
2+Or Si
4+By Al
3+Isomorphous substitution, thereby crystal layer is electronegative.Superfluous negative charge is by being free on the Na of interlayer
+, Ca
2+Keep charge balance, so sheet surfaces is adsorbed metallic cation easily.Polynite after the exchange is oleophilicity, and the distance between cheating engaging layer increases.
Layered double-hydroxide (LDHs, Mg
6Al
2(OH)
16CO
34H
2O) be a kind of natural mineral substance and the positively charged anion laminated material of interlayer, by mineral substance Mg (OH)
2Derive from.Its structure is by Mg (OH)
2Neutral line piles up and forms, and is positioned at a part of Mg on the layer
2+Can be by the Al of similar radius
3+Isomorphous substitution makes interlayer positively charged.
No matter be polynite class synusia shape material or hydrotalcite, directly intercalation is processed matrix material in body material, also can handle the back intercalation through modification and in body material, process matrix material, has better comprehensive performance.
Below further specify technology of the present invention and characteristics through specific embodiment, be intended to help the reader to understand technical spirit of the present invention and the beneficial effect that can produce better, can not be interpreted as qualification to practical range of the present invention.Among the present invention, except that indicating especially, said ratio and content are part by weight and content.
In the present embodiment 1, be outside steel pipe, to be coated with to make corrosion protection coating of the present invention, detailed process comprises:
The modification of hydrotalcite: get 10gMg-Al-LDH, be dissolved in the 300ml boiling and (remove CO
2) liquid in (deionized water: ethanol=1: 1, volume percent), be transferred in the there-necked flask then; Under 80 ℃ of magnetic agitation of water-bath, add the sodium metavanadate solution 100ml of 0.1M, stirring reaction is 2 hours under reflux temperature; Regulate with the 0.1M sodium hydroxide solution then and make pH value of solution=8.4; In the room temperature naturally cooling, spinning is cleaned 3 times with ethanol and water mixed liquid (volume percent 1: 1) with the relief reaction product; 200 mesh sieves were ground in 80 ℃ of vacuum-drying 24 hours.Through measuring, the Zeta potential of resultant powder is 12mV.
To be equivalent to resin quality per-cent and be 3% modified hydrotalcite powder joins in the mixture of bisphenol A type epoxy resin/resol (E51/F51) (mass percent is 6: 4); Obtained resin/hydrotalcite mixture solution in 2 hours 80 ℃ of quick down stirrings, subsequent use.
Adopt planetary ball mill with solidifying agent trimellitic acid 1,2-anhydride TMA and thinner 1, the 2-cylohexanediol diglycidyl ether was according to 1: 0.5 mass ratio ball mill mixing, and is subsequent use.Solidifying agent after resin matrix behind the above-mentioned intercalation and the dilution is ground evenly according to 1: 0.3 mass percent; Obtain coating; Manual application is in the steel pipe outside surface that cleans (rust cleaning, oil removing) immediately; Promptly get the anion-selective layer behind 80 ℃/4h+150 ℃/1h+180 ℃/4h hot setting, thickness is 150 μ m.
The modification of polynite: take by weighing 10gMMT and be scattered in the 300ml deionized water and form suspension-s, stirring at room makes its homodisperse; The properties-correcting agent nitrocalcite powder that will be equivalent to the polynite cation exchange capacity and be 110meq/100g joins in the above-mentioned solution, and in 80 ℃ of water-baths, constant temperature stirred 3 hours.After stirring, above-mentioned solution is poured in the acetone soln of 500ml, at room temperature stirred half a hour; Naturally cooling, spinning is cleaned 3 times with ethanol and water mixed liquid (volume percent 1: 1); 200 mesh sieves were ground in 80 ℃ of vacuum-drying 24 hours, made the polynite of modification.Through measuring, the Zeta potential of resulting powder is-20mV.
Be equivalent to resin quality per-cent and be 3% modified montmorillonoid and join (mass percent is 6: 4) in bisphenol A type epoxy resin/resol (E51/F51) mixture, stir fast down at 80 ℃ and obtained resin/polynite mixture solution in 2 hours, subsequent use.
Adopt planetary ball mill with solidifying agent trimellitic acid 1,2-anhydride TMA and thinner 1, the 2-cylohexanediol diglycidyl ether was according to 1: 0.5 mass ratio ball mill mixing, and is subsequent use.Solidifying agent after resin behind the intercalation and the dilution is ground evenly according to 1: 0.3 mass percent; Obtain coating; Manual application is outside the above-mentioned anion-selective of solidified layer immediately; Promptly get negative and positive type ion selectivity coating or film (be that internal layer is the anion-selective layer, skin is the cation selective layer) after waiting to solidify, the about 300 μ m of coating or film total thickness.
Thereby, outside steel pipe, form have ion barrier and optionally heat-resistant anticorrosive coating or film of the present invention.
Also adopt electrochemical impedance spectroscopy (EIS) method that the antiseptic property of this negative and positive type ion selectivity coating or film is tested among the present invention; Electrochemical impedance spectroscopy adopts the CHI660C electrochemical workstation; Under open circuit potential, measure, test frequency is 100kHz～0.01Hz, and amplitude is 20mV.Test macro is a three-electrode system, and sample is a working electrode, and SCE is a reference electrode, and carbon-point is a supporting electrode, and electrolytic solution is 5% sodium chloride solution, 90 ℃ of tests down.Compare with common ring oxygen coating or film (the about 300 μ m of thickness).Constant for guaranteeing concentration of electrolyte, change the electrolytic solution in the electrolyzer every day.Test result sees also Fig. 1, Fig. 2 a, Fig. 2 b and Fig. 3.Wherein, Fig. 1 shows the impedance-frequency relation of the different soak times of common ring oxygen coating; Fig. 2 a is the impedance-frequency relation of single cation selective coating and the different soak times of anion-selective coating with Fig. 2 b, and Fig. 3 is the impedance-frequency relation of the different soak times of negative and positive type ion selectivity coating of the present invention.Can find out that from the result its resistance value of common ring oxygen coating prolongation in time descends rapidly, the preservative effect of single ion selectivity coating is better than common epoxy coat, and wherein the preservative effect of cation selective coating is better than anionic.And that negative and positive type ion selectivity coating of the present invention changes its resistance value in time is almost constant, has good antiseptic property.
The coating or the film that soak the later stage are taken out from solution, carry out mechanically peel, utilize ESEM (SEM) to observe and metallic contact microscopic appearance at the interface.Fig. 4 shows the microscopic appearance and the energy spectrum analysis of common ring oxygen coating, can find that Na appears in coating or film surface
+And Cl
-, explain that corrosive medium arrives the metallic surface through coating or film, coating or film have lost iris action.Fig. 5 is coating or the film xsect microscopic appearance that refractory coating of the present invention soaks the later stage, can find that coating or film surface do not have Na
+And Cl
-, explain that this coating has to intercept the function that zwitterion penetrates into coating simultaneously to have preservative effect preferably.
Also use proportioning separate application on polyfluortetraethylene plate of described yin, yang ion selective layer to prepare anion-selective membrane, cation selective film in the present embodiment 1 simultaneously; Film thickness is about 100 μ m respectively; It is carried out the membrane potential test, and compare with epoxy resin film.Test result is as shown in Figure 6., can make that the removable ion that has heterocharge in the solution passes through, and repel the ion of band identical charges owing to there is fixed charge in ion selective membrane of the present invention inside.When there is the same electrolyte of different concns the both sides of ion selective membrane, will produce membrane potential at the interface at ion selective membrane.For anion-selective membrane, portion's fixed charge is a positively charged ion within it, so this film makes the removable negatively charged ion in the solution pass through, and repels positively charged ion, and membrane potential is for just; Cation selective film situation is opposite, and membrane potential is for negative.
The coating production of present embodiment 2 is the same with embodiment 1, and just electrolyte solution changes 90 ℃ of 5% hydrochloric acid soln into, and all the other test conditions are the same.
Test result sees also Fig. 7, Fig. 8 a, Fig. 8 b and Fig. 9.Fig. 7 shows the impedance-frequency relation of the different soak times of common ring oxygen coating; Fig. 8 a is the impedance-frequency relation of single cation selective coating and the different soak times of anion-selective coating with Fig. 8 b; Impedance-frequency relation when Fig. 9 is the different soak time of negative and positive polarity ion selectivity coating of the present invention.Can find that its resistance value of common ring oxygen coating prolongation in time descends rapidly, the preservative effect of single ion selectivity coating is better than common epoxy coat, and wherein the preservative effect of cation selective coating is better than anionic; And coating of the present invention descends slowly at the immersion process middle impedance, still is higher than 10 at immersion later stage resistance value
10Ω has the performance of acid resistance medium preferably.
The preparation method of the coating of present embodiment 3 is the same with embodiment 1, at the antiseptic property of having investigated coating under the simulated condition condition in the high temperature and high pressure kettle.Test conditions is: 135 ℃ of temperature in the kettle, corrosive medium are 5% Klorvess Liquid, stagnation pressure 2MPa in the still, H
2S partial pressure 0.4MPa, CO
2Dividing potential drop 1.6MPa utilizes the high pure nitrogen deoxygenation, test period 5 days.
Utilize ESEM and power spectrum that corrosion product is carried out morphology observation and composition analysis, test result is referring to Figure 10 a-10d.SEM figure shows that lower floor is the one side of adjacent metal among the figure, and the upper strata is the one side of direct crevice corrosion medium.The pure epoxy coating is soaked the back serious swelling is taken place, and coating lost efficacy; Cation selective coating and metal interface place have only potassium ion not have cl ions; Anion-selective coating and metal interface place have only cl ions not have potassium ion; Negative and positive polarity ion selectivity coating of the present invention and metal interface place had not both had cl ions not have potassium ion yet, had confirmed that the coating among the present invention has the ability of two-way choice.
The result of embodiments of the invention result and prior art is contrasted discovery; Embodiments of the invention are investigated is the destruction to coating of high-temperature acidic or neutral solution; And prior art generally all is to investigate the influence of normal temperature neutral solution to coating, and therefore result of the present invention shows that this coating has high thermal resistance and medium corrosion resistance preferably.
Claims (9)
1. ion barrier and selectivity heat-resistant anticorrosive coating composition, said composition comprises:
Can form the positively charged synusia shape inorganic materials and the body material of interlayer of anion-selective layer; And
Can form the electronegative synusia shape inorganic materials and the body material of interlayer of cation selective layer.
2. ion barrier and selectivity heat-resistant anticorrosive coating, this coating comprises:
The anion-selective layer, said anion-selective layer is formed by interlayer positively charged synusia shape inorganic materials and body material; And
The cation selective layer, said cation selective layer is formed by interlayer electronegative synusia shape inorganic materials and body material.
3. heat-resistant anticorrosive coating according to claim 2, wherein, the electro kinetic potential of the synusia shape inorganic materials that said interlayer is positively charged is greater than 0 with smaller or equal to 50mV; The electro kinetic potential of the synusia shape inorganic materials that interlayer is electronegative is less than 0 with more than or equal to-50mV.
4. heat-resistant anticorrosive coating according to claim 2, wherein, said body material is epoxy resin, resol, vinyl resin or polyamide polymers material.
5. heat-resistant anticorrosive coating according to claim 2, wherein, the electronegative synusia shape inorganic materials of said interlayer is polynite or the polynite after modification is handled; The positively charged synusia shape inorganic materials of interlayer is hydrotalcite or the hydrotalcite after modification is handled.
6. heat-resistant anticorrosive coating according to claim 2, wherein, the thickness of said anion-selective layer is 100～200 μ m, the thickness of said cation selective layer is 100～200 μ m.
7. method for preparing each described ion barrier of claim 2～6 and selectivity heat-resistant anticorrosive coating, this method comprises:
Behind synusia shape inorganic materials intercalation first body material that interlayer is positively charged, mix with first solidifying agent, coating forms the anion-selective layer again; Then, behind synusia shape inorganic materials intercalation second body material that interlayer is electronegative, mix with second solidifying agent, coating forms the cation selective layer again, wherein coating cation selective layer on the anion-selective layer.
8. the purposes of each described heat-resistant anticorrosive coating of claim 2～6 in metallic substance is anticorrosion.
9. the method for anticorrosion treatment of a metallic substance, this method comprises: the surface at metallic substance forms each described ion barrier of claim 2～6 and selectivity heat-resistant anticorrosive coating.
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