CN103642365A - Aluminium alloy corrosion self-repair intelligent coating for boats and preparation method thereof - Google Patents
Aluminium alloy corrosion self-repair intelligent coating for boats and preparation method thereof Download PDFInfo
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- CN103642365A CN103642365A CN201310577339.3A CN201310577339A CN103642365A CN 103642365 A CN103642365 A CN 103642365A CN 201310577339 A CN201310577339 A CN 201310577339A CN 103642365 A CN103642365 A CN 103642365A
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- aluminium alloy
- pyrroles
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 68
- 238000005260 corrosion Methods 0.000 title claims abstract description 68
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 51
- 239000011246 composite particle Substances 0.000 claims abstract description 28
- 150000002500 ions Chemical class 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000000084 colloidal system Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims description 50
- 229920000128 polypyrrole Polymers 0.000 claims description 50
- 150000003233 pyrroles Chemical class 0.000 claims description 46
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 41
- -1 fluorine titanium Chemical compound 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 23
- 239000004593 Epoxy Substances 0.000 claims description 21
- 125000003700 epoxy group Chemical group 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 14
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N Sodium molybdate Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N Sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- KAESVJOAVNADME-UHFFFAOYSA-N pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract description 4
- 230000001590 oxidative Effects 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 8
- 229910052681 coesite Inorganic materials 0.000 abstract 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract 4
- 229910052904 quartz Inorganic materials 0.000 abstract 4
- 239000000377 silicon dioxide Substances 0.000 abstract 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract 4
- 229910052682 stishovite Inorganic materials 0.000 abstract 4
- 229910052905 tridymite Inorganic materials 0.000 abstract 4
- 239000011258 core-shell material Substances 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000002987 primer (paints) Substances 0.000 description 21
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 238000005488 sandblasting Methods 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 210000002356 Skeleton Anatomy 0.000 description 3
- 229910000424 chromium(II) oxide Inorganic materials 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000003628 erosive Effects 0.000 description 3
- 239000011294 coal tar pitch Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 231100000078 corrosive Toxicity 0.000 description 2
- 231100001010 corrosive Toxicity 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 230000000873 masking Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229920002521 Macromolecule Polymers 0.000 description 1
- 240000007119 Malus pumila Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005039 chemical industry Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 101700066231 nas-30 Proteins 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011528 polyamide (building material) Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
The invention discloses an aluminium alloy corrosion self-repair intelligent coating for boats and a preparation method thereof, and belongs to the technical field of metal corrosion-resistant intelligent coatings. The coating employs the following method for preparation: (1) putting fluorotitanate ion, fluozirconate ion, pyrrole and an oxidant in a nanometer SiO2 colloid medium to perform pyrrole chemical oxidation polymerization, so as to obtain a core-shell structural fluorotitanate/ fluozirconate doped polypyrolle coated nanometer SiO2 composite colloid, performing separation, drying and crushing under the vacuum condition, so as to obtain core-shell structural fluorotitanate/ fluozirconate doped polypyrolle coated nanometer SiO2 composite particles; and (2) taking the obtained core-shell structural fluorotitanate/ fluozirconate doped polypyrolle coated nanometer SiO2 composite particles as a corrosion self-repair component, doping into an aluminium alloy primer for boats, and spraying on an aluminium alloy substrate to obtain the coating. The coating not only has intelligent corrosion self-repair effect, but also helps to obviously improve the corrosion resistance and the service of the aluminium alloy for boats, and is environment friendly.
Description
Technical field
The present invention relates to 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.
Background technology
At present, the marine aluminium alloy primer coating chromic salt fillers (as zinc yellow) that contain carinogenicity danger that use, to strengthen corrosion resistance coating and application sticking power more.
Chromic salt filler can form chromate passivation film with aluminium alloy, and its skeleton is Cr
2o
3and Zn (CrO
2)
2etc. insoluble Cr (III) oxide compound (or salt), in skeleton, be filled with Cr (VI) oxide compound (or salt) of solubility.After coating water suction, Cr (VI) oxide compound (or salt) will be gradually forms CrO from stripping in skeleton
3; When corrosive medium penetrates rete arrival aluminium alloy matrix surface formation point corrosion pit, CrO
3can again generate new film and cover point corrosion pit with the Al-alloy based precursor reactant exposing, stop it to further expand, thereby make coating there is intelligence corrosion self-repair function, further extend to a certain extent coating service life.
Yet along with the increasingly stringent of environmental regulation, the use of chromic salt filler is subject to the generally restriction of our times various countries.The novel intelligent corrosion coatings selfreparing component of therefore, seeking to have good environmental-protecting performance becomes the task of top priority to replace current heavily contaminated chromic salt filler.Yet, there is no up to now the non-chromate component that can make coating there is the effect of corrosion Smart self-repairing and occur.
Conductive polymers is through chemistry or the electrochemical doping method family macromolecule material that to make it be conductor by insulator transition by the polymer with conjugatedπbond.It is except having metal and semi-conductive conductive characteristic, also have that high molecular molecular structure can design, can process, low density advantage, this makes conductive polymers all demonstrate application prospect widely in fields such as electrode materials, photoelectromagnetism material, sensor, corrosion prevention and life sciences.Compare with other conducting high polymers things, conducting high polymers thing-polypyrrole (polypyrrole with conjugated double bond, PPy) due to synthetic convenient, specific conductivity is high, good stability, be easy to film forming, advantages of environment protection, has more caused people's extensive concern.
The electroconductibility of eigenstate polypyrrole is poor, must adulterate to strengthen its conductivity.Doped polypyrrole mechanism comprises redox doping and protonic acid doping, and its essence is the electronics in π track to be pulled out to (p-type doping) or electronics is added to (N-shaped doping) in π unoccupied orbital, can change by state, and it is poor to reduce to be with.Steady state under polypyrrole room temperature is the conductive doped state of its p-type, and this doping state has reduction (dedoping) and reoxidizes (doping) characteristic, and doped polypyrrole is reacted and can be expressed as with dedoping:
Pyrrole monomer polymerization process mainly contains chemical oxidative polymerization and electrochemical polymerization method, because electrochemically oxidative polymerization gained polypyrrole film is insoluble molten and workability is poor, has limited its application aspect metallic corrosion protection.For this field, should adopt chemical oxidising polymerisation gained polypyrrole powder introducing organic resin is prepared into the method for compound coating, but need improve its dispersion stabilization in masking liquid.The people such as M.G.Han are once with inorganic nano SiO
2as dispersion agent, prepare and be polyaniline/nanometer SiO that colloidal state disperses
2matrix material, provides new approaches for improving the workability of conductive polymers.The polypyrrole clad nano SiO if prepare thus, with nucleocapsid structure
2composite gel can improve the dispersion stabilization of polypyrrole in masking liquid equally.
In addition, about being there are to benzene sulfonate, carboxylate salt, molybdate etc. in the doping type of negatively charged ion in oxidizable pyrrole polymerization process.For example, the people such as G.Paliwoda-Porebska has studied the corrosion self-repair function mechanism of phosphomolybdate Doped polypyrrole for iron-based body.This mechanism thinks, when iron-based body corrosion potential reduces, dedoping reaction can occur polypyrrole, and discharges molybdate and phosphoric acid salt, makes the pH value rising of metal/polymer interface and forms local passive film with iron-based body, thereby can delay the corrosion of iron-based body.
Thus, if the negatively charged ion (as fluorine titanium/zirconate) alloy matrix aluminum to the effect of corrosion inhibition is introduced to pyrroles's polymerization process, simultaneously with nanometer SiO
2for being coated with, core improves polypyrrole dispersion stabilization, then by the nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO obtaining after vacuum separation, dry also fragmentation
2composite particles is when the marine aluminium alloy coating enhancement component, and fluorine titanium/zirconate ion can form and take the fine and close chemical conversion film of nano level that titanium/zirconium composite hydrous oxide is main ingredient with aluminium alloy.When the corrosion of aluminium alloy germinating stage, when corrosion potential reduces, just can there is dedoping reaction and discharge part fluorine titanium/zirconate ion in polypyrrole, and again form local passive film with corrosion place aluminium alloy, thereby make coating there is intelligence corrosion self-repair function, effectively improve solidity to corrosion and the service life of coating.But this technology there is no relevant report at present.
Summary of the invention
The problem serious for the marine aluminium alloy primer coating environmental pollution at present with corrosion Smart self-repairing function, marine aluminium alloy primer coating that adopt non-chromate component does not possess again corrosion Smart self-repairing function, 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 erosion resistance and the service life of marine aluminium alloy, and environmental friendliness.
Object of the present invention is realized by following technical scheme:
A 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 SiO
2the preparation of composite particles
Hydrofluotitanic acid root, fluorine zirconate, pyrroles and four kinds of components of oxygenant are placed in to nanometer SiO
2in colloidal medium, carry out pyrroles's chemical oxidising polymerisation, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite gel; Under vacuum condition, carry out separation, dry and broken, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles;
(2) with obtained nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles, as corrosion selfreparing component, is doped in marine aluminium alloy priming paint and sprays on alloy matrix aluminum, obtains marine aluminium alloy corrosion selfreparing smart coat of the present invention;
Wherein, using hydrofluotitanic acid root and fluorine zirconate as to negatively charged ion in step (1), hydrofluotitanic acid root is 0.02～5.0:1 with the amount of substance ratio of fluorine zirconate, preferably 0.1～2.5:1, more preferably 0.2～1.0:1; To negatively charged ion, be 0.05～0.5:1 with pyrroles's amount of substance ratio, preferably 0.1～0.4:1, more preferably 0.2～0.3:1; Described oxygenant is iron nitrate, hydrogen peroxide, Sodium Persulfate, Sodium orthomolybdate or sodium wolframate, and pyrroles is 0.5～5.0:1 with the amount of substance ratio of oxygenant, 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%, SiO
2with pyrroles's amount of substance ratio be 1.0～50:1, preferably 5.0～30:1, more preferably 10～20:1;
Be preferably-the 0.09MPa of vacuum tightness of vacuum condition described in step (1);
Described in step (1), pyrroles's chemical oxidising polymerisation condition is: temperature of reaction is 60～80 ℃, and the reaction times 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 SiO
2composite particles particle diameter is 20～100 μ m, preferably 30～70 μ m;
Marine aluminium alloy priming paint base resin used described in step (2) is that modified resin, the acrylic based resin of the modified resin of epoxy, epoxy, organic silicone, organic silicone are, the modified resin of modified resin, Vinylite or the Vinylite of acrylic based resin, preferably epoxy;
When described in step (2), marine aluminium alloy priming paint base resin used is epoxy, the adulterated total mass of marine aluminium alloy priming paint of corrosion selfreparing component of take is 100%, and wherein each component and quality percentage composition are as follows:
Described auxiliary agent is the conventional auxiliary agent of paint field;
The total solids part quality of corrosion selfreparing component and marine aluminium alloy priming paint of take is 100%, and wherein, the quality of corroding selfreparing component described in step (2) accounts for the 0.5wt%～20wt% of total solids part quality, preferably 1wt%～10wt%, more preferably 3wt%～7wt%.
Beneficial effect
The method of the invention is the negatively charged ion (as fluorine titanium/zirconate) alloy matrix aluminum to the effect of corrosion inhibition is introduced to pyrroles's polymerization process, simultaneously with nanometer SiO
2for core is coated with on the basis of improving polypyrrole dispersion stabilization, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles, and using this composite particles as marine aluminium alloy primer coating corrosion selfreparing component, water in corrosive medium enters after coating, in the corrosion of aluminium alloy germinating stage, alloy matrix aluminum corrosion potential reduces, bring out the reaction of polypyrrole generation dedoping and discharge part fluorine titanium/zirconate ion, and form and take the fine and close chemical conversion film of nano level that titanium/zirconium composite hydrous oxide is main ingredient with aluminium alloy, thereby make coating there is intelligence corrosion self-repair function, significantly improve erosion resistance and the service life of coating, the present situation that does not possess corrosion Smart self-repairing function to overcome current non-chromate component.And described coating does not contain chromic salt component, environmental friendliness.
Embodiment
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, coat-thickness is recorded by coating thickness detector.
Middle temperature coal tar pitch is warm coal tar pitch in 1#, Henan Bao Shun Chemical Industry Science Co., Ltd;
Flake aluminum slurry is 30 μ m flake aluminum slurries, Guangxi pingguo Xin Da Industrial Co., Ltd.;
Polymeric amide is ATUREX650 polyamide curing agent, Jiangxi Ai Tu Rake Industrial Co., Ltd.;
Nanometer SiO
2colloid is NAS-30 silicon sol, Shanghai Xiang Lan Chemical Co., Ltd..
Embodiment 1
Using hydrofluotitanic acid root and fluorine zirconate as to negatively charged ion, and hydrogen peroxide is oxygenant, potassium fluotitanate: potassium fluozirconate: 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 the nanometer SiO that solid content is 30wt%
2in colloidal medium, carry out pyrroles's chemical oxidising polymerisation, wherein SiO
2than being 15:1, pyrroles's chemical oxidising polymerisation condition is at 70 ℃, to react 5h with pyrroles's amount of substance, and pH value is 2.8, obtains nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite gel, and in SZG-200 type band crushing cutter DoubletaperedVacuumdrier, carry out separation, dry and broken, vacuum tightness is-0.09MPa that obtaining particle diameter is nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO of 40 μ m
2composite particles.
With above-mentioned nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles, as corrosion selfreparing component, is doped in marine aluminium alloy epoxy primer, and the coating obtaining is composed as follows:
By above-mentioned coating through sandblasting rear surface roughness R
aon the AA5083 alloy matrix aluminum of>=1.6 μ m, spray, obtain marine aluminium alloy corrosion selfreparing smart coat of the present invention, coat-thickness is 300 μ m.Wherein corrode the 5wt% that selfreparing component accounts for coating total solids part quality.
For comparing, adopt and be not coated the nanometer SiO processing
2colloid is as primer coating selfreparing component, and all the other are identical with the present embodiment, on the AA5083 alloy matrix aluminum through sandblasting, sprays, and obtaining thickness is the conventional marine aluminium alloy epoxy primer coating of 300 μ m.
Embodiment 2
Using hydrofluotitanic acid root and fluorine zirconate as to negatively charged ion, and Sodium orthomolybdate is oxygenant, potassium fluotitanate: potassium fluozirconate: pyrroles: the amount of substance of Sodium orthomolybdate is than being 1:1:6.67:3.33.Above-mentioned four kinds of components are placed in to the nanometer SiO that solid content is 40wt%
2in colloidal medium, carry out pyrroles's chemical oxidising polymerisation, wherein SiO
2than being 20:1, pyrroles's chemical oxidising polymerisation condition is at 80 ℃, to react 6h with pyrroles's amount of substance, and pH value is 2.5, obtains nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite gel, and in SZG-200 type band crushing cutter DoubletaperedVacuumdrier, carry out separation, dry and broken, vacuum tightness is-0.09MPa that obtaining particle diameter is nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO of 30 μ m
2composite particles.
With above-mentioned nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles, as corrosion selfreparing component, is doped in marine aluminium alloy epoxy primer, and the coating obtaining is composed as follows:
By above-mentioned coating through sandblasting rear surface roughness R
aon the AA5A06 alloy matrix aluminum of>=1.6 μ m, spray, obtain marine aluminium alloy corrosion selfreparing smart coat of the present invention, coat-thickness is 300 μ m.Wherein corrode the 7wt% that selfreparing component accounts for coating total solids part quality.
For comparing, adopt and be not coated the nanometer SiO processing
2colloid is as primer coating selfreparing component, and all the other are identical with the present embodiment, on the AA5A06 alloy matrix aluminum through sandblasting, sprays, and obtaining thickness is the conventional marine aluminium alloy epoxy primer coating of 300 μ m.
Embodiment 3
Using hydrofluotitanic acid root and fluorine zirconate as to negatively charged ion, and iron nitrate is oxygenant, potassium fluotitanate: potassium fluozirconate: pyrroles: the amount of substance of iron nitrate is than being 1:5:30:20.Above-mentioned four kinds of components are placed in to the nanometer SiO that solid content is 30wt%
2in colloidal medium, carry out pyrroles's chemical oxidising polymerisation, wherein SiO
2than being 10:1, pyrroles's chemical oxidising polymerisation condition is at 60 ℃, to react 3h with pyrroles's amount of substance, and pH value is 3.0, obtains nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite gel, and in SZG-200 type band crushing cutter DoubletaperedVacuumdrier, carry out separation, dry and broken, vacuum tightness is-0.09MPa that obtaining particle diameter is nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO of 70 μ m
2composite particles.
With above-mentioned nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles, as corrosion selfreparing component, is doped in marine aluminium alloy epoxy primer, and the coating obtaining is composed as follows:
By above-mentioned coating through sandblasting rear surface roughness R
aon the AA6061 alloy matrix aluminum of>=1.6 μ m, spray, obtain marine aluminium alloy corrosion selfreparing smart coat of the present invention, coat-thickness is 300 μ m.Wherein corrode the 3wt% that selfreparing component accounts for coating total solids part quality.
For comparing, adopt and be not coated the nanometer SiO processing
2colloid is as primer coating selfreparing component, and all the other are identical with the present embodiment, on the AA6061 alloy matrix aluminum through sandblasting, sprays, and obtaining thickness is the conventional marine aluminium alloy epoxy primer coating of 300 μ m.
Embodiment 4
Using hydrofluotitanic acid root and fluorine zirconate as to negatively charged ion, and sodium wolframate is oxygenant, potassium fluotitanate: potassium fluozirconate: pyrroles: the amount of substance of sodium wolframate is than being 1:1.5:10:7.Above-mentioned four kinds of components are placed in to the nanometer SiO that solid content is 35wt%
2in colloidal medium, carry out pyrroles's chemical oxidising polymerisation, wherein SiO
2than being 18:1, pyrroles's chemical oxidising polymerisation condition is at 60 ℃, to react 4.5h with pyrroles's amount of substance, and pH value is 2.6, obtains nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite gel, and in SZG-200 type band crushing cutter DoubletaperedVacuumdrier, carry out separation, dry and broken, vacuum tightness is-0.09MPa that obtaining particle diameter is nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO of 50 μ m
2composite particles.
With above-mentioned nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles, as corrosion selfreparing component, is doped in marine aluminium alloy epoxy primer, and the coating obtaining is composed as follows:
By above-mentioned coating through sandblasting rear surface roughness R
aon the AA6061 alloy matrix aluminum of>=1.6 μ m, spray, obtain marine aluminium alloy corrosion selfreparing smart coat of the present invention, coat-thickness is 300 μ m.Wherein corrode the 4wt% that selfreparing component accounts for coating total solids part quality.
For comparing, adopt and be not coated the nanometer SiO processing
2colloid is as primer coating selfreparing component, and all the other are identical with the present embodiment, on the AA6061 alloy matrix aluminum through sandblasting, sprays, and obtaining thickness is the conventional marine aluminium alloy epoxy primer coating of 300 μ m.
Embodiment 5
Using hydrofluotitanic acid root and fluorine zirconate as to negatively charged ion, and Sodium Persulfate is oxygenant, potassium fluotitanate: potassium fluozirconate: pyrroles: the amount of substance of Sodium Persulfate is than being 1:3:18:10.Above-mentioned four kinds of components are placed in to the nanometer SiO that solid content is 30wt%
2in colloidal medium, carry out pyrroles's chemical oxidising polymerisation, wherein SiO
2than being 16:1, pyrroles's chemical oxidising polymerisation condition is at 70 ℃, to react 4h with pyrroles's amount of substance, and pH value is 2.9, obtains nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite gel, and in SZG-200 type band crushing cutter DoubletaperedVacuumdrier, carry out separation, dry and broken, vacuum tightness is-0.09MPa that obtaining particle diameter is nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO of 40 μ m
2composite particles.
With above-mentioned nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles, as corrosion selfreparing component, is doped in marine aluminium alloy epoxy primer, and the coating obtaining is composed as follows:
By above-mentioned coating through sandblasting rear surface roughness R
aon the AA5086 alloy matrix aluminum of>=1.6 μ m, spray, obtain marine aluminium alloy corrosion selfreparing smart coat of the present invention, coat-thickness is 300 μ m.Wherein corrode the 5wt% that selfreparing component accounts for coating total solids part quality.
For comparing, adopt and be not coated the nanometer SiO processing
2colloid is as primer coating selfreparing component, and all the other are identical with the present embodiment, on the AA5086 alloy matrix aluminum through sandblasting, sprays, and obtaining thickness is the conventional marine aluminium alloy epoxy primer coating of 300 μ m.
According to ASTM B117-2009 standard, by the conventional marine aluminium alloy epoxy primer coating of embodiment 1～5 preparation as a comparative example, and the prepared corrosion selfreparing smart coat sample of embodiment 1～5 be placed in respectively YWX/Q-250B type salt-spray cabinet and carry out 3000h neutral salt spray test (NSS).According to GB/T6461-2002 standard, to testing rear print extent of corrosion grade, evaluate, result is as shown in table 1:
After table 1.NSS3000h, sample corrosion class is evaluated (R
p)
| Sequence number | Embodiment grade | Comparative example grade |
| 1 | 10 | 6 |
| 2 | 9 | 5 |
| 3 | 9 | 4 |
| 4 | 8 | 4 |
| 5 | 10 | 7 |
Test-results shows, the marine aluminium alloy corrosion selfreparing smart coat extent of corrosion grade that the present invention prepares, apparently higher than existing marine aluminium alloy epoxy primer coating, can obviously improve erosion resistance and the service life of marine aluminium alloy coating.
The present invention includes but be not limited to above embodiment, every any being equal to of carrying out under the principle of spirit of the present invention, replaces 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, described coating adopts following methods to prepare:
(1) nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2the preparation of composite particles
Hydrofluotitanic acid root, fluorine zirconate, pyrroles and four kinds of components of oxygenant are placed in to nanometer SiO
2in colloidal medium, carry out pyrroles's chemical oxidising polymerisation, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite gel; Under vacuum condition, carry out separation, dry and broken, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles;
(2) with obtained nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles, as corrosion selfreparing component, is doped in marine aluminium alloy priming paint and sprays on alloy matrix aluminum, obtains described marine aluminium alloy corrosion selfreparing smart coat;
Wherein, in step (1), using hydrofluotitanic acid root and fluorine zirconate as to negatively charged ion, hydrofluotitanic acid root is 0.02～5.0:1 with the amount of substance ratio of fluorine zirconate, to negatively charged ion, be 0.05～0.5:1 with pyrroles's amount of substance ratio, described oxygenant is iron nitrate, hydrogen peroxide, Sodium Persulfate, Sodium orthomolybdate or sodium wolframate, and pyrroles is 0.5～5.0:1 with the amount of substance ratio of oxygenant;
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: temperature of reaction is 60～80 ℃, and the reaction times 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 SiO
2composite particles particle diameter is 20～100 μ m;
The total solids part quality of corrosion selfreparing component and marine aluminium alloy priming paint of take is 100%, and wherein, the quality of corroding selfreparing component described in step (2) accounts for the 0.5wt%～20wt% of total solids part quality;
Marine aluminium alloy priming paint base resin used described in step (2) is that modified resin, the acrylic based resin of the modified resin of epoxy, epoxy, organic silicone, organic silicone are, the modified resin of modified resin, Vinylite or the Vinylite of acrylic based resin.
2. the preparation method that marine aluminium alloy corrodes selfreparing smart coat as claimed in claim 1, is characterized in that, described method steps is as follows:
(1) nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2the preparation of composite particles
Hydrofluotitanic acid root, fluorine zirconate, pyrroles and four kinds of components of oxygenant are placed in to nanometer SiO
2in colloidal medium, carry out pyrroles's chemical oxidising polymerisation, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite gel; Under vacuum condition, carry out separation, dry and broken, obtain nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles;
(2) with obtained nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles, as corrosion selfreparing component, is doped in marine aluminium alloy priming paint and sprays on alloy matrix aluminum, obtains described marine aluminium alloy corrosion selfreparing smart coat;
Wherein, in step (1), using hydrofluotitanic acid root and fluorine zirconate as to negatively charged ion, hydrofluotitanic acid root is 0.02～5.0:1 with the amount of substance ratio of fluorine zirconate, to negatively charged ion, be 0.05～0.5:1 with pyrroles's amount of substance ratio, described oxygenant is iron nitrate, hydrogen peroxide, Sodium Persulfate, Sodium orthomolybdate or sodium wolframate, and pyrroles is 0.5～5.0:1 with the amount of substance ratio of oxygenant;
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: temperature of reaction is 60～80 ℃, and the reaction times 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 SiO
2composite particles particle diameter is 20～100 μ m;
The total solids part quality of corrosion selfreparing component and marine aluminium alloy priming paint of take is 100%, and wherein, the quality of corroding selfreparing component described in step (2) accounts for the 0.5wt%～20wt% of total solids part quality;
Marine aluminium alloy priming paint base resin used described in step (2) is that modified resin, the acrylic based resin of the modified resin of epoxy, epoxy, organic silicone, organic silicone are, the modified resin of modified resin, Vinylite or the Vinylite of acrylic based resin.
3. the preparation method that a kind of marine aluminium alloy according to claim 2 corrodes selfreparing smart coat, it is characterized in that, in step (1), hydrofluotitanic acid root is 0.1～2.5:1 with the amount of substance ratio of fluorine zirconate, to negatively charged ion, be 0.1～0.4:1 with pyrroles's amount of substance ratio, pyrroles is 1.0～3.0:1 with the amount of substance ratio of oxygenant.
4. the preparation method that a kind of marine aluminium alloy according to claim 2 corrodes selfreparing smart coat, it is characterized in that, hydrofluotitanic acid root is 0.2～1.0:1 with the amount of substance ratio of fluorine zirconate, to negatively charged ion, be 0.2～0.3:1 with pyrroles's amount of substance ratio, pyrroles is 1.5～2.0:1 with the amount of substance ratio of oxygenant.
5. the preparation method of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2, is characterized in that nanometer SiO described in step (1)
2colloid solid content is 30～40wt%, SiO
2with pyrroles's amount of substance ratio be 5.0～30:1.
6. the preparation method of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2, is characterized in that SiO described in step (1)
2with pyrroles's amount of substance ratio be 10～20:1.
7. the preparation method of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2, is characterized in that, described in step (1), the vacuum tightness of vacuum condition is-0.09MPa, described nucleocapsid structure fluorine titanium/zirconic acid Doped polypyrrole clad nano SiO
2composite particles particle diameter is 30～70 μ m.
8. the preparation method of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2, is characterized in that, the quality of corroding selfreparing component described in step (2) accounts for the 1wt%～10wt% of total solids part quality.
9. the preparation method of a kind of marine aluminium alloy corrosion selfreparing smart coat according to claim 2, is characterized in that, the quality of corroding selfreparing component described in step (2) accounts for the 3wt%～7wt% of total solids part quality.
10. the preparation method that a kind of marine aluminium alloy according to claim 2 corrodes selfreparing smart coat, it is characterized in that, described in step (2), marine aluminium alloy priming paint base resin used is epoxy, the adulterated total mass of marine aluminium alloy priming paint of corrosion selfreparing component of take is 100%, and wherein each component and quality percentage composition are as follows:
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