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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
aluminium alloy
pyrroles
selfreparing
corrosion
amount
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201310577339.3A
Other languages
Chinese (zh)
Other versions
CN103642365B (en
Inventor
刘斌
方志刚
王虹斌
管勇
黎理胜
刘立洁
王涛
严川伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NO92537 UNIT OF PEOPLE'S LIBERATION ARMY
Original Assignee
NO92537 UNIT OF PEOPLE'S LIBERATION ARMY
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NO92537 UNIT OF PEOPLE'S LIBERATION ARMY filed Critical NO92537 UNIT OF PEOPLE'S LIBERATION ARMY
Priority to CN201310577339.3A priority Critical patent/CN103642365B/en
Publication of CN103642365A publication Critical patent/CN103642365A/en
Application granted granted Critical
Publication of CN103642365B publication Critical patent/CN103642365B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

A kind of marine aluminium alloy corrosion selfreparing smart coat and preparation method thereof
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:
CN201310577339.3A 2013-11-18 2013-11-18 A kind of marine aluminium alloy corrosion selfreparing smart coat and preparation method thereof Active CN103642365B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310577339.3A CN103642365B (en) 2013-11-18 2013-11-18 A kind of marine aluminium alloy corrosion selfreparing smart coat and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310577339.3A CN103642365B (en) 2013-11-18 2013-11-18 A kind of marine aluminium alloy corrosion selfreparing smart coat and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103642365A true CN103642365A (en) 2014-03-19
CN103642365B CN103642365B (en) 2016-05-18

Family

ID=50247658

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310577339.3A Active CN103642365B (en) 2013-11-18 2013-11-18 A kind of marine aluminium alloy corrosion selfreparing smart coat and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103642365B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105524497A (en) * 2016-01-06 2016-04-27 南京理工大学 Superhydrophobic self-healing intelligent nano-coating and preparation method thereof
CN107674467A (en) * 2016-11-18 2018-02-09 中国科学院海洋研究所 A kind of marine organisms base selfreparing anticorrosive paint and preparation method thereof
CN108326511A (en) * 2017-12-27 2018-07-27 中车唐山机车车辆有限公司 A kind of aluminum alloy railway vehicle manufacturing method
CN113047229A (en) * 2020-12-29 2021-06-29 武汉力拓桥科防撞设施有限公司 Novel anti-ship-collision facility with self-lubricating property and corrosion resistance

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6054514A (en) * 1997-05-20 2000-04-25 Americhem, Inc. Additives for enhancing corrosion protection of metals
EP1382721A1 (en) * 2002-07-08 2004-01-21 The Boeing Company Coating for inhibiting oxidation of a substrate
CN101035630A (en) * 2004-08-03 2007-09-12 坎梅陶尔股份有限公司 Process for coating metallic surfaces with an anti-corrosive coating
CN102382550A (en) * 2011-09-08 2012-03-21 哈尔滨工程大学海洋装备科技有限公司 Solvent-free epoxy anticorrosion paint with corrosion restoration function and preparation method thereof
CN102634266A (en) * 2012-04-27 2012-08-15 天津翔盛粉末涂料有限公司 Weather-resistant heavy-duty anticorrosive powder coating
CN103360908A (en) * 2013-07-22 2013-10-23 天长市银狐漆业有限公司 Epoxy coal tar pitch paint

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6054514A (en) * 1997-05-20 2000-04-25 Americhem, Inc. Additives for enhancing corrosion protection of metals
EP1382721A1 (en) * 2002-07-08 2004-01-21 The Boeing Company Coating for inhibiting oxidation of a substrate
CN101035630A (en) * 2004-08-03 2007-09-12 坎梅陶尔股份有限公司 Process for coating metallic surfaces with an anti-corrosive coating
CN102382550A (en) * 2011-09-08 2012-03-21 哈尔滨工程大学海洋装备科技有限公司 Solvent-free epoxy anticorrosion paint with corrosion restoration function and preparation method thereof
CN102634266A (en) * 2012-04-27 2012-08-15 天津翔盛粉末涂料有限公司 Weather-resistant heavy-duty anticorrosive powder coating
CN103360908A (en) * 2013-07-22 2013-10-23 天长市银狐漆业有限公司 Epoxy coal tar pitch paint

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
张莉等: "浅析环氧煤焦沥青涂料的研究现状及进展", 《涂料技术与文摘》, vol. 30, no. 10, 31 October 2009 (2009-10-31) *
许均等: "聚吡咯/SiO2作导电助剂的水性环氧抗静电涂料的制备", 《涂料工业》, vol. 35, no. 6, 30 June 2005 (2005-06-30), pages 30 - 33 *
许均等: "聚吡咯/二氧化硅复合材料的制备及导电性的研究", 《化学与黏合》, vol. 27, no. 1, 31 January 2005 (2005-01-31), pages 1 - 4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105524497A (en) * 2016-01-06 2016-04-27 南京理工大学 Superhydrophobic self-healing intelligent nano-coating and preparation method thereof
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
CN107674467A (en) * 2016-11-18 2018-02-09 中国科学院海洋研究所 A kind of marine organisms base selfreparing anticorrosive paint and preparation method thereof
CN107674467B (en) * 2016-11-18 2020-02-21 中国科学院海洋研究所 Marine organism-based self-repairing anticorrosive coating and preparation method thereof
CN108326511A (en) * 2017-12-27 2018-07-27 中车唐山机车车辆有限公司 A kind of aluminum alloy railway vehicle manufacturing method
CN113047229A (en) * 2020-12-29 2021-06-29 武汉力拓桥科防撞设施有限公司 Novel anti-ship-collision facility with self-lubricating property and corrosion resistance

Also Published As

Publication number Publication date
CN103642365B (en) 2016-05-18

Similar Documents

Publication Publication Date Title
Deshpande et al. Conducting polymers for corrosion protection: a review
CN104893489B (en) A kind of one-component salt spray resistance water paint and preparation method thereof
CN105623473A (en) Zinc-containing graphene anti-corrosive primer based on graphene dispersoid
CN105623471A (en) Epoxy resin-graphene-zinc powder anticorrosive coating and preparation method thereof
CN103642365B (en) A kind of marine aluminium alloy corrosion selfreparing smart coat and preparation method thereof
CN101407690A (en) Bi-component epoxy zinc rich primer
CN101418182B (en) Conductive macromolecule solvent-free low viscosity anti-corrosive paint and preparation method thereof
CN1290940C (en) Anti-corrosion paint for metal with improved corrosion resistance
CN105348870A (en) Preparation method of chromium-free dacromet coating
CN108948964A (en) Single-walled carbon nanotube reinforced epoxy zinc rich primer and preparation method thereof
CN102604514B (en) Pollution-free aqueous antirust coating
CN107474615A (en) A kind of anti-corrosion self-healing coatings
CN101368055A (en) Silicone hydride and polyaniline hybridized polymer watersoluble metal heavy anticorrosion paint
CN105585939A (en) Self-repairing coating with rust conversion function and preparation method thereof
CN107805798A (en) Graphene prefilming agent and its preparation and application before coated metal
CN1935911B (en) Bottom-surface-in-one fluorocarbon enamelled paint and its preparing method
CN101717608B (en) Conductive anti-corrosion coating of electric power grounding grid and preparation method thereof
CN106752708A (en) A kind of epoxy mild steel valve anticorrosive paint and preparation method thereof
CN101680095A (en) Non-chromium containing black multi-layer coatings
CN103254736B (en) A kind of have Polyaniline powder paint of acid resistance self-repair function and preparation method thereof
CN1803951A (en) Aqueous polyanion metal composite anti-corrosion material and method for preparing the same
CN104745044A (en) Zinc-rich primer using activation technique
CN110305580A (en) A kind of graphene-based hydrophobic type anticorrosive coating and its preparation method and application
CN105778060A (en) Water-dispersed polythiophene for aqueous anticorrosive paint and preparation method of water-dispersed polythiophene
CN109836871A (en) A kind of preparation method of graphene composite material and a kind of polymer coating

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant