CN103642365B - A kind of marine aluminium alloy corrosion selfreparing smart coat and preparation method thereof - Google Patents
A kind of marine aluminium alloy corrosion selfreparing smart coat and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of marine aluminium alloy corrosion selfreparing smart coat and preparation method thereof, belong to the corrosion-resistant smart coat technical field of metal. Described coating adopts following methods preparation: fluotitanic acid root, fluorine zirconate, pyrroles and oxidant are placed in nanometer SiO by (1)2In colloidal medium, carry out pyrroles's chemical oxidising polymerisation, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite colloid; Under vacuum condition, separate, dry and broken, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles; (2) with obtained nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles, as corrosion selfreparing component, is doped in marine aluminium alloy priming paint and sprays on alloy matrix aluminum, obtains described coating. Described coating not only has intelligence corrosion self-repair function, can obviously improve corrosion resistance and the service life of marine aluminium alloy, and environmental friendliness.
Description
Technical field
The present invention relates to a kind of marine aluminium alloy corrosion selfreparing smart coat and preparation method thereof, belong to metalCorrosion-resistant smart coat technical field.
Background technology
At present, the marine aluminium alloy primer coating chromate fillers (as zinc yellow) that contain carcinogenicity danger that use more,To strengthen corrosion resistance coating and application adhesive force.
Chromate filler can form chromate passivation film with aluminium alloy, and its skeleton is Cr2O3And Zn (CrO2)2DengInsoluble Cr (III) oxide (or salt), is filled with Cr (VI) oxide (or salt) of solubility in skeleton.When after coating water suction, Cr (VI) oxide (or salt) will be gradually forms CrO from stripping in skeleton3; Work as corruptionWhen erosion medium penetrates rete arrival aluminium alloy matrix surface formation point corrosion pit, CrO3Can again close with the aluminium exposingAuri precursor reactant generates new film and covers point corrosion pit, stops it to further expand, thereby makes coating have intelligenceCan corrode self-repair function, further extend to a certain extent coating service life.
But along with the increasingly stringent of environmental regulation, the use of chromate filler is subject to our times various countriesGenerally restriction. Therefore, seek to have the novel intelligent corrosion coatings selfreparing group of good environmental-protecting performanceDivide and become the task of top priority to replace current heavily contaminated chromate filler. But, there is no up to now and can make coatingThe non-chromate component with the effect of corrosion Smart self-repairing occurs.
Conducting polymer is to make it by absolutely by the macromolecule with conjugatedπbond through chemistry or electrochemical doping methodEdge body changes a family macromolecule material of conductor into. It except thering is metal and semi-conductive conductive characteristic,Also have that high molecular molecular structure can design, can process, low density advantage, this exists conducting polymerThe fields such as electrode material, photoelectromagnetic material, sensor, corrosion protection and life science all demonstrate widelyApplication prospect. Compared with other conducting high polymers things, there is the conducting high polymers thing of conjugated double bond-polypyrrole (polypyrrole, PPy) due to synthetic convenient, electrical conductivity is high, good stability, be easy to film forming,Advantages of environment protection, has caused people's extensive concern more.
The electric conductivity of eigenstate polypyrrole is poor, must adulterate to strengthen its electric conductivity. Polypyrrole is mixedAssorted mechanism comprises redox doping and protonic acid doping, and its essence is by the electronics pull-out (p-type in π trackDoping) or electronics is added to (N-shaped doping) in π unoccupied orbital, can change by state, reduce energyIt is poor to be with. Stable state under polypyrrole room temperature is the conductive doped state of its p-type, and it is (de-that this doping state has reductionDoping) and reoxidize (doping) characteristic, doped polypyrrole is reacted and can be expressed as with dedoping:
Pyrrole monomer polymerization mainly contains chemical oxidative polymerization and electrochemical polymerization method, due to electrochemistry oxygenChange polymerization gained polypyrrole film insoluble molten and machinability is poor, limited it aspect metal erosion protectionApplication. Should adopt chemical oxidising polymerisation gained polypyrrole powder is introduced to organic resin system for this fieldThe method of standby one-tenth composite coating, but need improve its dispersion stabilization in masking liquid. The people such as M.G.Han once withInorganic nano SiO2Prepare and be polyaniline/nanometer SiO that colloidal state disperses as dispersant2Composite,For the machinability of improving conducting polymer provides new approaches. Thus, there is nucleocapsid structure if preparePolypyrrole clad nano SiO2Composite colloid can improve the dispersion stabilization of polypyrrole in masking liquid equally.
In addition, there is benzene sulfonate, carboxylic about the doping type to anion in oxidizable pyrrole polymerization processHydrochlorate, molybdate etc. For example, the people such as G.Paliwoda-Porebska has studied phosphomolybdate Doped polypyrroleFor the corrosion self-repair function mechanism of iron-based body. This mechanism is thought, poly-pyrrole when iron-based body corrosion potential reducesCough up dedoping reaction can occur, and discharge molybdate and phosphate, make metal/polymer interface pH valueRise and form local passivating film with iron-based body, thereby can delay the corrosion of iron-based body.
Thus, if the anion (as fluorine titanium/zirconate) alloy matrix aluminum to the effect of corrosion inhibition is drawnEnter pyrroles's polymerization process, simultaneously with nanometer SiO2For being coated with, core improves polypyrrole dispersion stabilization, soAfter by the nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano obtaining after vacuum separation, dry and fragmentationSiO2Composite particles strengthens when component for marine aluminium alloy coating, fluorine titanium/zirconate ion can with aluminium alloy shapeBecome the fine and close chemical composition coating of nanoscale taking titanium/zirconium composite hydrous oxide as key component. Work as corrosion of aluminium alloyIn the germinating stage, when corrosion potential reduces, just can there is dedoping reaction and discharge part fluorine titanium/zirconic acid in polypyrroleRadical ion, and again form local passivating film with corrosion place aluminium alloy, thus make coating there is intelligence corrosion certainlyRepair, effectively improves corrosion resistance and the service life of coating. But this technology there is no relevant report at present.
Summary of the invention
Serious for the marine aluminium alloy primer coating environmental pollution at present with corrosion Smart self-repairing function,Adopt the marine aluminium alloy primer coating of non-chromate component not possess again asking of corrosion Smart self-repairing functionTopic, the object of the present invention is to provide a kind of marine aluminium alloy corrosion selfreparing smart coat and preparation method thereof,Adopt the coating that described method prepares not only to there is intelligence corrosion self-repair function, can obviously improve peculiar to vesselThe corrosion resistance of aluminium alloy and service life, and environmental friendliness.
Object of the present invention is realized by following technical scheme:
A kind of marine aluminium alloy corrosion selfreparing smart coat, described coating adopts following methods to prepare:
(1) nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2The preparation of composite particles
Fluotitanic acid root, fluorine zirconate, pyrroles and four kinds of components of oxidant are placed in to nanometer SiO2In colloidal mediumCarry out pyrroles's chemical oxidising polymerisation, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2CompoundColloid; Under vacuum condition, separate, dry and broken, obtain the poly-pyrrole of nucleocapsid structure fluorine titanium/zirconic acid dopingCough up clad nano SiO2Composite particles;
(2) with obtained nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles conductCorrosion selfreparing component, is doped in marine aluminium alloy priming paint and sprays on alloy matrix aluminum, obtains thisBright described marine aluminium alloy corrosion selfreparing smart coat;
Wherein, in step (1) using fluotitanic acid root and fluorine zirconate as to anion, fluotitanic acid root and fluorine zirconiumThe amount of substance ratio of acid group is 0.02～5.0:1, preferably 0.1～2.5:1, more preferably 0.2～1.0:1; RightAnion is 0.05～0.5:1 with pyrroles's amount of substance ratio, preferably 0.1～0.4:1, and more preferably 0.2～0.3:1; Described oxidant is ferric nitrate, hydrogen peroxide, sodium peroxydisulfate, sodium molybdate or sodium tungstate, pyrroles and oxidantAmount of substance ratio be 0.5～5.0:1, preferably 1.0～3.0:1, more preferably 1.5～2.0:1;
Nanometer SiO described in step (1)2Colloid solid content is preferably 30～40wt%, SiO2With pyrroles'sAmount of substance ratio is 1.0～50:1, preferably 5.0～30:1, more preferably 10～20:1;
Be preferably-the 0.09MPa of vacuum of vacuum condition described in step (1);
Described in step (1), pyrroles's chemical oxidising polymerisation condition is: reaction temperature is 60～80 DEG C, reactionTime is 3～6h, and pH value is 2.5～3.0;
The Doped polypyrrole of nucleocapsid structure fluorine titanium/zirconic acid described in step (1) clad nano SiO2Composite particles grainFootpath is 20～100 μ m, preferably 30～70 μ m;
Described in step (2), marine aluminium alloy priming paint base resin used is epoxy, epoxyModified resin, organic silicone, the modified resin of organic silicone, acrylic based resin, propyleneThe modified resin of modified resin, vinylite or the vinylite of acidic group resin, preferably epoxy;
In the time that described in step (2), marine aluminium alloy priming paint base resin used is epoxy, to adulterateThe gross mass of marine aluminium alloy priming paint of corrosion selfreparing component be 100%, wherein each component and quality hundredDivide content as follows:
Described auxiliary agent is the conventional auxiliary agent of paint field;
Taking total solid part quality of corrosion selfreparing component and marine aluminium alloy priming paint as 100%, wherein, stepThe quality of suddenly corroding selfreparing component described in (2) accounts for the 0.5wt%～20wt% of total solid part quality, excellentSelect 1wt%～10wt%, more preferably 3wt%～7wt%.
Beneficial effect
The method of the invention by anion alloy matrix aluminum to the effect of corrosion inhibition (as fluorine titanium/zirconiumAcid group) introduce pyrroles's polymerization process, simultaneously with nanometer SiO2For being coated with, core improves polypyrrole dispersion surelyBasis is upper qualitatively, obtains nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles, andThe corrosion selfreparing component using this composite particles as marine aluminium alloy primer coating, when the water in corrosive medium entersEnter after coating, in the corrosion of aluminium alloy germinating stage, alloy matrix aluminum corrosion potential reduces, and brings out polypyrroleThere is dedoping reaction and discharge part fluorine titanium/zirconate ion, and form with the compound hydration of titanium/zirconium with aluminium alloyOxide is the fine and close chemical composition coating of the nanoscale of key component, thereby makes coating have intelligence corrosion selfreparingAct on, significantly improve corrosion resistance and the service life of coating, do not possess to overcome current non-chromate componentThe present situation of corrosion Smart self-repairing function. And described coating does not contain chromate component, environmental friendliness.
Detailed description of the invention
Below in conjunction with specific embodiment in detail the present invention is described in detail, but is not limited to this.
Described in following examples, coating layer thickness is recorded by coating thickness detector.
Middle temperature coal tar pitch is warm coal tar pitch in 1#, Henan Baoshun Chemical Technology Co., Ltd.;
Flake aluminum slurry is 30 μ m flake aluminum slurries, Xin Da Industrial Co., Ltd. of Guangxi pingguo;
Polyamide is ATUREX650 polyamide curing agent, Jiangxi Ai Tu Rake Industrial Co., Ltd.;
Nanometer SiO2Colloid is NAS-30 Ludox, Shanghai Xiang Lan Chemical Co., Ltd..
Embodiment 1
Using fluotitanic acid root and fluorine zirconate as to anion, hydrogen peroxide is oxidant, potassium fluotitanate: fluorine zirconiumAcid potassium: pyrroles: the amount of substance of hydrogen peroxide is than being 1:2:12:6.87. Above-mentioned four kinds of components are placed in to solid contentFor the nanometer SiO of 30wt%2In colloidal medium, carry out pyrroles's chemical oxidising polymerisation, wherein SiO2Thing with pyrrolesThe amount of matter is than being 15:1, and pyrroles's chemical oxidising polymerisation condition is at 70 DEG C, to react 5h, and pH value is 2.8,Obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite colloid, and at SZG-200 type bandIn crushing cutter double conic rotary vacuum dryer, separate, dry and broken, vacuum is-0.09MPa, obtainsObtaining particle diameter is nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO of 40 μ m2Composite particles.
With above-mentioned nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles is reviewed one's lessons by oneself as corrosionMultiple component, is doped in marine aluminium alloy epoxy primer, and the coating obtaining is composed as follows:
By above-mentioned coating through blasting treatment rear surface roughness RaThe AA5083 alloy matrix aluminum of >=1.6 μ mOn spray, obtain marine aluminium alloy of the present invention corrosion selfreparing smart coat, coating layer thickness is300 μ m. Wherein corrode the 5wt% that selfreparing component accounts for coating total solid part quality.
For comparing, adopt and be not coated the nanometer SiO processing2Colloid is as primer coating selfreparing groupPoint, all the other are identical with the present embodiment, on the AA5083 alloy matrix aluminum through blasting treatment, spray,Obtaining thickness is the conventional marine aluminium alloy epoxy primer coating of 300 μ m.
Embodiment 2
Using fluotitanic acid root and fluorine zirconate as to anion, sodium molybdate is oxidant, potassium fluotitanate: fluorine zirconiumAcid potassium: pyrroles: the amount of substance of sodium molybdate is than being 1:1:6.67:3.33. Above-mentioned four kinds of components are placed in admittedly and are containedAmount is the nanometer SiO of 40wt%2In colloidal medium, carry out pyrroles's chemical oxidising polymerisation, wherein SiO2With pyrroles'sAmount of substance is than being 20:1, and pyrroles's chemical oxidising polymerisation condition is at 80 DEG C, to react 6h, and pH value is 2.5,Obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite colloid, and at SZG-200 type bandIn crushing cutter double conic rotary vacuum dryer, separate, dry and broken, vacuum is-0.09MPa, obtainsObtaining particle diameter is nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO of 30 μ m2Composite particles.
With above-mentioned nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles is reviewed one's lessons by oneself as corrosionMultiple component, is doped in marine aluminium alloy epoxy primer, and the coating obtaining is composed as follows:
By above-mentioned coating through blasting treatment rear surface roughness RaThe AA5A06 alloy matrix aluminum of >=1.6 μ mOn spray, obtain marine aluminium alloy of the present invention corrosion selfreparing smart coat, coating layer thickness is300 μ m. Wherein corrode the 7wt% that selfreparing component accounts for coating total solid part quality.
For comparing, adopt and be not coated the nanometer SiO processing2Colloid is as primer coating selfreparing groupPoint, all the other are identical with the present embodiment, on the AA5A06 alloy matrix aluminum through blasting treatment, spray,Obtaining thickness is the conventional marine aluminium alloy epoxy primer coating of 300 μ m.
Embodiment 3
Using fluotitanic acid root and fluorine zirconate as to anion, ferric nitrate is oxidant, potassium fluotitanate: fluorine zirconiumAcid potassium: pyrroles: the amount of substance of ferric nitrate is than being 1:5:30:20. Above-mentioned four kinds of components are placed in to solid content isThe nanometer SiO of 30wt%2In colloidal medium, carry out pyrroles's chemical oxidising polymerisation, wherein SiO2Material with pyrrolesAmount than for 10:1, pyrroles's chemical oxidising polymerisation condition is at 60 DEG C, to react 3h, pH value is 3.0, obtainsObtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite colloid, and broken at SZG-200 type bandIn broken cutter double conic rotary vacuum dryer, separate, dry and broken, vacuum be-0.09MPa, acquisitionParticle diameter is nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO of 70 μ m2Composite particles.
With above-mentioned nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles is reviewed one's lessons by oneself as corrosionMultiple component, is doped in marine aluminium alloy epoxy primer, and the coating obtaining is composed as follows:
By above-mentioned coating through blasting treatment rear surface roughness RaThe AA6061 alloy matrix aluminum of >=1.6 μ mOn spray, obtain marine aluminium alloy of the present invention corrosion selfreparing smart coat, coating layer thickness is300 μ m. Wherein corrode the 3wt% that selfreparing component accounts for coating total solid part quality.
For comparing, adopt and be not coated the nanometer SiO processing2Colloid is as primer coating selfreparing groupPoint, all the other are identical with the present embodiment, on the AA6061 alloy matrix aluminum through blasting treatment, spray,Obtaining thickness is the conventional marine aluminium alloy epoxy primer coating of 300 μ m.
Embodiment 4
Using fluotitanic acid root and fluorine zirconate as to anion, sodium tungstate is oxidant, potassium fluotitanate: fluorine zirconiumAcid potassium: pyrroles: the amount of substance of sodium tungstate is than being 1:1.5:10:7. Above-mentioned four kinds of components are placed in to solid contentFor the nanometer SiO of 35wt%2In colloidal medium, carry out pyrroles's chemical oxidising polymerisation, wherein SiO2Thing with pyrrolesThe amount of matter is than being 18:1, and pyrroles's chemical oxidising polymerisation condition is at 60 DEG C, to react 4.5h, and pH value is 2.6,Obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite colloid, and at SZG-200 type bandIn crushing cutter double conic rotary vacuum dryer, separate, dry and broken, vacuum is-0.09MPa, obtainsObtaining particle diameter is nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO of 50 μ m2Composite particles.
With above-mentioned nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles is reviewed one's lessons by oneself as corrosionMultiple component, is doped in marine aluminium alloy epoxy primer, and the coating obtaining is composed as follows:
By above-mentioned coating through blasting treatment rear surface roughness RaThe AA6061 alloy matrix aluminum of >=1.6 μ mOn spray, obtain marine aluminium alloy of the present invention corrosion selfreparing smart coat, coating layer thickness is300 μ m. Wherein corrode the 4wt% that selfreparing component accounts for coating total solid part quality.
For comparing, adopt and be not coated the nanometer SiO processing2Colloid is as primer coating selfreparing groupPoint, all the other are identical with the present embodiment, on the AA6061 alloy matrix aluminum through blasting treatment, spray,Obtaining thickness is the conventional marine aluminium alloy epoxy primer coating of 300 μ m.
Embodiment 5
Using fluotitanic acid root and fluorine zirconate as to anion, sodium peroxydisulfate is oxidant, potassium fluotitanate: fluorinePotassium zirconium: pyrroles: the amount of substance of sodium peroxydisulfate is than being 1:3:18:10. Above-mentioned four kinds of components are placed in admittedly and are containedAmount is the nanometer SiO of 30wt%2In colloidal medium, carry out pyrroles's chemical oxidising polymerisation, wherein SiO2With pyrroles'sAmount of substance is than being 16:1, and pyrroles's chemical oxidising polymerisation condition is at 70 DEG C, to react 4h, and pH value is 2.9,Obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite colloid, and at SZG-200 type bandIn crushing cutter double conic rotary vacuum dryer, separate, dry and broken, vacuum is-0.09MPa, obtainsObtaining particle diameter is nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO of 40 μ m2Composite particles.
With above-mentioned nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles is reviewed one's lessons by oneself as corrosionMultiple component, is doped in marine aluminium alloy epoxy primer, and the coating obtaining is composed as follows:
By above-mentioned coating through blasting treatment rear surface roughness RaThe AA5086 alloy matrix aluminum of >=1.6 μ mOn spray, obtain marine aluminium alloy of the present invention corrosion selfreparing smart coat, coating layer thickness is300 μ m. Wherein corrode the 5wt% that selfreparing component accounts for coating total solid part quality.
For comparing, adopt and be not coated the nanometer SiO processing2Colloid is as primer coating selfreparing groupPoint, all the other are identical with the present embodiment, on the AA5086 alloy matrix aluminum through blasting treatment, spray,Obtaining thickness is the conventional marine aluminium alloy epoxy primer coating of 300 μ m.
According to ASTMB117-2009 standard, at the bottom of the conventional marine aluminium alloy epoxy of embodiment 1～5 preparationAs a comparative example, and the prepared corrosion selfreparing smart coat sample of embodiment 1～5 is placed in respectively lacquer coatIn YWX/Q-250B type salt spray test chamber, carry out 3000h neutral salt spray test (NSS). According to GB/T6461-2002 standard is evaluated testing rear print extent of corrosion grade, and result is as shown in table 1:
After table 1.NSS3000h, sample corrosion class is evaluated (Rp)
| Sequence number | Embodiment grade | Comparative example grade |
| 1 | 10 | 6 |
| 2 | 9 | 5 |
| 3 | 9 | 4 |
| 4 | 8 | 4 |
| 5 | 10 | 7 |
Result of the test shows, the marine aluminium alloy corrosion selfreparing smart coat corrosion journey that the present invention preparesDegree grade, apparently higher than existing marine aluminium alloy epoxy primer coating, can obviously improve marine aluminium alloy coatingCorrosion resistance and service life.
The present invention includes but be not limited to above embodiment, every appointing of carrying out under the principle of spirit of the present inventionHow with replacing or local improvement, all will be considered as within protection scope of the present invention.
Claims (10)
1. a marine aluminium alloy corrosion selfreparing smart coat, is characterized in that, below described coating adoptsMethod prepares:
(1) nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2The preparation of composite particles
Fluotitanic acid root, fluorine zirconate, pyrroles and four kinds of components of oxidant are placed in to nanometer SiO2In colloidal mediumCarry out pyrroles's chemical oxidising polymerisation, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2CompoundColloid; Under vacuum condition, separate, dry and broken, obtain the poly-pyrrole of nucleocapsid structure fluorine titanium/zirconic acid dopingCough up clad nano SiO2Composite particles;
(2) with obtained nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles conductCorrosion selfreparing component, is doped in marine aluminium alloy priming paint and sprays on alloy matrix aluminum, described in acquisitionMarine aluminium alloy corrosion selfreparing smart coat;
Wherein, in step (1) using fluotitanic acid root and fluorine zirconate as to anion, fluotitanic acid root and fluorine zirconiumThe amount of substance ratio of acid group is 0.02～5.0:1, is 0.05～0.5 to anion with pyrroles's amount of substance ratio:1, described oxidant is ferric nitrate, hydrogen peroxide, sodium peroxydisulfate, sodium molybdate or sodium tungstate, pyrroles and oxidantAmount of substance ratio be 0.5～5.0:1;
SiO described in step (1)2With pyrroles's amount of substance ratio be 1.0～50:1;
Described in step (1), pyrroles's chemical oxidising polymerisation condition is: reaction temperature is 60～80 DEG C, reactionTime is 3～6h, and pH value is 2.5～3.0;
The Doped polypyrrole of nucleocapsid structure fluorine titanium/zirconic acid described in step (1) clad nano SiO2Composite particles grainFootpath is 20～100 μ m;
Taking total solid part quality of corrosion selfreparing component and marine aluminium alloy priming paint as 100%, wherein, stepThe quality of suddenly corroding selfreparing component described in (2) accounts for the 0.5wt%～20wt% of total solid part quality;
Described in step (2), marine aluminium alloy priming paint base resin used is epoxy, epoxyModified resin, organic silicone, the modified resin of organic silicone, acrylic based resin, propyleneThe modified resin of modified resin, vinylite or the vinylite of acidic group resin.
2. the preparation method that marine aluminium alloy corrodes selfreparing smart coat as claimed in claim 1, itsBe characterised in that, described method step is as follows:
(1) nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2The preparation of composite particles
Fluotitanic acid root, fluorine zirconate, pyrroles and four kinds of components of oxidant are placed in to nanometer SiO2In colloidal mediumCarry out pyrroles's chemical oxidising polymerisation, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2CompoundColloid; Under vacuum condition, separate, dry and broken, obtain the poly-pyrrole of nucleocapsid structure fluorine titanium/zirconic acid dopingCough up clad nano SiO2Composite particles;
(2) with obtained nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles conductCorrosion selfreparing component, is doped in marine aluminium alloy priming paint and sprays on alloy matrix aluminum, described in acquisitionMarine aluminium alloy corrosion selfreparing smart coat;
Wherein, in step (1) using fluotitanic acid root and fluorine zirconate as to anion, fluotitanic acid root and fluorine zirconiumThe amount of substance ratio of acid group is 0.02～5.0:1, is 0.05～0.5 to anion with pyrroles's amount of substance ratio:1, described oxidant is ferric nitrate, hydrogen peroxide, sodium peroxydisulfate, sodium molybdate or sodium tungstate, pyrroles and oxidantAmount of substance ratio be 0.5～5.0:1;
SiO described in step (1)2With pyrroles's amount of substance ratio be 1.0～50:1;
Described in step (1), pyrroles's chemical oxidising polymerisation condition is: reaction temperature is 60～80 DEG C, reactionTime is 3～6h, and pH value is 2.5～3.0;
The Doped polypyrrole of nucleocapsid structure fluorine titanium/zirconic acid described in step (1) clad nano SiO2Composite particles grainFootpath is 20～100 μ m;
Taking total solid part quality of corrosion selfreparing component and marine aluminium alloy priming paint as 100%, wherein, stepThe quality of suddenly corroding selfreparing component described in (2) accounts for the 0.5wt%～20wt% of total solid part quality;
Described in step (2), marine aluminium alloy priming paint base resin used is epoxy, epoxyModified resin, organic silicone, the modified resin of organic silicone, acrylic based resin, propyleneThe modified resin of modified resin, vinylite or the vinylite of acidic group resin.
3. the preparation side of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2Method, is characterized in that, in step (1), fluotitanic acid root is 0.1～2.5:1 with the amount of substance ratio of fluorine zirconate,Be 0.1～0.4:1 to anion with pyrroles's amount of substance ratio, pyrroles with the amount of substance ratio of oxidant is1.0～3.0：1。
4. the preparation side of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2Method, is characterized in that, fluotitanic acid root is 0.2～1.0:1 with the amount of substance ratio of fluorine zirconate, to anionWith pyrroles's amount of substance ratio be 0.2～0.3:1, pyrroles is 1.5～2.0:1 with the amount of substance ratio of oxidant.
5. the preparation side of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2Method, is characterized in that, nanometer SiO described in step (1)2Colloid solid content is 30～40wt%, SiO2With pyrroles's amount of substance ratio be 5.0～30:1.
6. the preparation side of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2Method, is characterized in that, SiO described in step (1)2With pyrroles's amount of substance ratio be 10～20:1.
7. the preparation side of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2Method, is characterized in that, described in step (1), the vacuum of vacuum condition is-0.09MPa, described nucleocapsid knotStructure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO2Composite particles particle diameter is 30～70 μ m.
8. the preparation side of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2Method, is characterized in that, the quality of corroding selfreparing component described in step (2) accounts for 1 of total solid part qualitywt%～10wt%。
9. the preparation side of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2Method, is characterized in that, the quality of corroding selfreparing component described in step (2) accounts for 3 of total solid part qualitywt%～7wt%。
10. the preparation side of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2Method, is characterized in that, described in step (2), marine aluminium alloy priming paint base resin used is epoxy,Taking the gross mass of the marine aluminium alloy priming paint of the corrosion selfreparing component of having adulterated as 100%, wherein each component andQuality percentage composition is as follows:
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| CN105524497B (en) * | 2016-01-06 | 2018-03-09 | 南京理工大学 | A kind of super-hydrophobic selfreparing intelligent nano coating and preparation method thereof |
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