CN102080224A - Cobaltous acetate-doped sol-gel film layer and preparation method thereof - Google Patents
Cobaltous acetate-doped sol-gel film layer and preparation method thereof Download PDFInfo
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- CN102080224A CN102080224A CN 201010586593 CN201010586593A CN102080224A CN 102080224 A CN102080224 A CN 102080224A CN 201010586593 CN201010586593 CN 201010586593 CN 201010586593 A CN201010586593 A CN 201010586593A CN 102080224 A CN102080224 A CN 102080224A
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Abstract
The invention provides a cobaltous acetate-doped sol-gel film layer and a preparation method thereof. In the sol system of the sol-gel film layer, zirconium isopropanol and gamma-glycidoxypropyltrimethoxysilane are used a precursors, absolute ethanol is used as a solvent, ethyl acetoacetate is used as a catalyst, and cobaltous acetate serving as an additive is doped in the sol system. The film is complete and compact and can provide a physical barrier for aluminum and aluminum alloy to prevent corrosive media from entering the aluminum and aluminum alloy, so that the corrosion reaction on the aluminum alloy is inhibited and the corrosion resistance of the aluminum alloy is improved; and the film also has high stability and durability, can exert a corrosion inhibition effect on damaged sol-gel films, and the corrosion inhibition effect can delay or even inhibit the damage of the corrosive media to the surfaces of metals.
Description
Technical field
The present invention relates to a kind of anticorrosion rete and preparation method of metallic substance, be specifically related to a kind of collosol and gel rete and preparation method of the cobaltous acetate that mixes, it is specially adapted to the corrosion prevention of aluminium and aluminium alloy.
Background technology
Aluminium and aluminium alloy be because its proportion is little, good processability, and conduction, heat conductivility is good, and plasticity is good, is easy to be shaped, and advantages such as low price are widely used in fields such as light industry, building materials, space flight, electronics.But, itself is corroded alloy matrix aluminum easily, needs it is carried out necessary surface treatment under a stable condition.
In view of tradition can be restricted environment is harmful for aluminium alloy provides the use of the chromic salt of corrosion resisting property, surrogate to chromic salt in several years has in the past carried out a large amount of research, wherein by on aluminium alloy, applying one deck collosol and gel rete, this tunic can provide one deck physical barriers for aluminum alloy specimen, entering of retardance corrosive medium, thereby suppressed the generation of corrosion reaction on the aluminium alloy, reached the corrosion resisting property that improves aluminium alloy.
Although the research to sol-gel film has obtained very big progress, have a large amount of datas to verify that sol-gel film improves to the corrosion protection tool of aluminium alloy, but this preventing mechanism is only just set up when the collosol and gel rete is excellent.When having a spot of defective to exist on the collosol and gel rete, this rete system then can not provide protection for exposed region.Therefore, provide corrosion protection not only to mean the rete that covers one deck densification for protection coating, also should provide corrosion inhibition, so that after the breakage of rete generation part, still can continue to provide barrier propterty.These performances can realize by add specific material in sol-gel system.When sol-gel film was destroyed, this additive still can provide corrosion protection for regional area.But the use of additive also can produce some side effects, and as reducing the stability of collosol and gel, molybdenum acid ion can reduce the stability of the network structure of collosol and gel, thereby reduces its corrosion resisting property.In addition, some additive is because of discharge making fast that from rete being not easy Be Controlled and solubility of additive also has significant effects to the secular corrosion protection of sol-gel film, is unsuitable for because of solubleness is too high as long-term protection as trivalent cerium.
The invention provides a kind of preparation technology of the cobaltous acetate collosol and gel rete that mixes, its addition is compared cerous low, and it not only can not destroy the integrity and the compactness of rete, and can improve the corrosion resisting property of collosol and gel rete.This in addition doping sol-gel film can also provide corrosion inhibition for the sol-gel film that is damaged.This be since cobalt ion when rete produces defective, the OH that generates with corrosion reaction on the one hand
-In conjunction with producing precipitation, cover (Al) on the negative electrode, played blocking action; And, also can be Co because acetate is weakly alkaline
2+Precipitin reaction takes place, and OH is provided
-On the other hand, because CH3COO
-Metal is had stronger adsorption and is preferentially adsorbed on aluminium alloy matrix surface, and Cl
-Competitive adsorption takes place make Cl
-Away from the aluminium surface, suppress the corrosive purpose thereby reach.
Summary of the invention
The collosol and gel rete and the preparation method that the purpose of this invention is to provide a kind of cobaltous acetate that mixes, this tunic is complete, fine and close, can provide one deck physical barriers for aluminium and aluminium alloy, entering of retardance corrosive medium, thereby suppressed the generation of corrosion reaction on the aluminium alloy, reached the corrosion resisting property that improves aluminium alloy; This tunic also has satisfactory stability and weather resistance, can provide corrosion inhibition for the sol-gel film that is damaged, and this corrosion inhibition can slow down even suppress the infringement that corrosive medium causes the metallic surface.
Collosol and gel rete employing zirconium iso-propoxide (TPOZ) (the n-propyl alcohol solution of 75wt.%) of the present invention and γ-Huan Yangbingyangbingjisanjiayangjiguiwan (GTMS) (〉=98wt.%) as presoma, the reagent that uses is all analytical pure.
The present invention adopts dehydrated alcohol as solvent.
The present invention adopts methyl aceto acetate as catalyzer, so that control the hydrolysis rate of organic zirconates.
The present invention adopts cobaltous acetate to be doped to sol system as additive.
Among the present invention cobaltous acetate is directly added in the sol system for preparing, stirring gets final product.
This invention is a kind of preparation method of the cobaltous acetate collosol and gel rete that mixes.The doping of cobaltous acetate not only can not destroy the integrity and the compactness of rete among the present invention, and can improve the corrosion resisting property of collosol and gel rete.This in addition doping sol-gel film can also provide corrosion inhibition for the sol-gel film that is damaged.The doping of cobaltous acetate is 0.01～0.5wt.% among the present invention, and preferred doping is 0.05～0.15wt.%.
Concrete implementation step is as follows:
1) pre-treatment of aluminium and aluminium alloy
1. polishing: adopt sand papering to 800#;
2. flow and wash from the beginning;
3. alkali cleaning: sodium hydroxide 55g/L, 50～60 ℃ of dipping 30s;
4. flow again after the hot water wash and wash from the beginning;
5. bright dipping: chromic acid: 110g/L; Nitric acid: 45g/L; Hydrofluoric acid: 22g/L;
6. flow and wash from the beginning.
2) preparation of colloidal sol
1. it is standby as solvent to adopt graduated cylinder to measure the 1L dehydrated alcohol;
2. the preparation of GTMS sol system: the GTMS of 60mL is slowly poured in an amount of solvent in the stirring, add excessive deionized water then, make the abundant hydrolysis of GTMS;
3. the preparation of TPOZ sol system: the employing methyl aceto acetate is a catalyzer, and at first the methyl aceto acetate with 13mL fully stirs with an amount of solvent, slowly adds the TPOZ of 26.7mL then; To be mixed evenly after, lentamente deionized water is dripped wherein, TPOZ and deionized water mol ratio are 3: 1;
4. above-mentioned two kinds of sol systems place respectively under the room temperature and stir 0.5h;
5. mix above-mentioned two kinds of sol systems, stir;
6. the cobaltous acetate of weighing certain mass fully is dissolved in it in proper amount of solvent, pours mixed sols then into, is mixed with the doping cobaltous acetate sol system of 0.05～0.15wt.% concentration;
7. add residual solvent under the whipped state in mixed sols, 2h is stirred in sealing.
3) preparation of collosol and gel rete
1. dip-coating: will impregnated in 100s in the sol system that configures through the aluminum alloy specimen of pre-treatment, and come out with the VELOCITY EXTRACTION of 1mm/s then;
2. surface drying: in air, place about 10min, place 60 ℃ to place 10min down again;
3. repeat 1. and 2. step the dip-coating 3 times repeatedly of every group of sample;
4. solidify with dry: place 110 ℃ of following 0.5h so that the rete complete drying.
The invention has the advantages that: preparation technology is simple, and treatment temp is low, and good uniformity is poisoned for a short time to environment and workmen, very strong society and economic worth are arranged; The collosol and gel thickness of preparation is about 8～9 μ m, this tunic does not cause rete inside demixing phenomenon to occur because of repeatedly applying, sol-gel film is kept perfectly on the whole, can provide one deck physical barriers for aluminum alloy specimen, thereby plays the effect of corrosion prevention; An amount of cobaltous acetate is doped to as additive is prepared into sol-gel film in the sol system, this layer doping has satisfactory stability and weather resistance, not only can improve corrosion resisting property for alloy matrix aluminum; Corrosion inhibition can also when being damaged, rete be provided.
Description of drawings
Fig. 1 is the cross section pattern (* 5000) of the sol-gel film of doping 0.5wt.% cobaltous acetate among the embodiment 4;
Fig. 2 is the polarization curve of doping different concns cobaltous acetate sol-gel film sample in 0.05M NaCl solution, drawing reference numeral 1 is the polarization curve of the sol-gel film sample that do not mix among the embodiment 1 among the figure, 2 is the polarization curve of the cobaltous acetate sample of doping 0.05wt.% among the embodiment 2,3 is the polarization curve of the cobaltous acetate sample of doping 0.15wt.% among the embodiment 3,4 is the polarization curve of the cobaltous acetate sample of doping 0.5wt.% among the embodiment 4, and this is to get by the polarization curve of testing the sol-gel film sample of the cobaltous acetate of doping different concns in 4 embodiments;
Fig. 3 is that doping different concns cobaltous acetate sol-gel film sample soaks the surface topography after 36 days in 0.05M NaCl solution, drawing reference numeral 1 is the surface topography of the sol-gel film sample that do not mix among the embodiment 1 among the figure, 2 is the surface topography of the cobaltous acetate sol-gel film sample of doping 0.05wt.% among the embodiment 2,3 is the surface topography of the cobaltous acetate sol-gel film sample of doping 0.15wt.% among the embodiment 3, and 4 is the surface topography of the cobaltous acetate sol-gel film sample of doping 0.5wt.% among the embodiment 4.This is that doping different concns cobaltous acetate sol-gel film sample soaks surface topography after 36 days in 4 embodiments in 0.05M NaCl solution.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
1) pre-treatment of aluminium and aluminium alloy
1. polishing: adopt sand papering to 800#;
2. flow and wash from the beginning;
3. alkali cleaning: sodium hydroxide 55g/L, 50～60 ℃ of dipping 30s;
4. flow again after the hot water wash and wash from the beginning;
5. bright dipping: chromic acid: 110g/L; Nitric acid: 45g/L; Hydrofluoric acid: 22g/L;
6. flow and wash from the beginning.
2) the do not mix preparation of colloidal sol
1. it is standby as colloidal sol to adopt graduated cylinder to measure the 1L dehydrated alcohol;
2. the preparation of GTMS sol system: the GTMS of 60mL is slowly poured in an amount of solvent in the stirring, add excessive deionized water then, make the abundant hydrolysis of GTMS;
3. the preparation of TPOZ sol system: the employing methyl aceto acetate is a catalyzer, and at first the methyl aceto acetate with 13mL fully stirs with an amount of solvent, slowly adds the TPOZ of 26.7mL then; To be mixed evenly after, lentamente deionized water is dripped wherein, TPOZ and deionized water mol ratio are 3: 1;
4. above-mentioned two kinds of sol systems place respectively under the room temperature and stir 0.5h;
5. mix above-mentioned two kinds of sol systems, add residual solvent under the whipped state in mixed sols, 2h is stirred in sealing.
3) preparation of collosol and gel rete
1. dip-coating: will impregnated in 100s in the sol system that configures through the aluminum alloy specimen of pre-treatment, and come out with the VELOCITY EXTRACTION of 1mm/s then;
2. surface drying: in air, place about 10min, place 60 ℃ to place 10min down again;
3. repeat 1. and 2. step the dip-coating 3 times repeatedly of every group of sample;
4. solidify with dry: place 110 ℃ of following 0.5h so that the rete complete drying.
1) pre-treatment of aluminium and aluminium alloy
Concrete treating processes is with embodiment 1.
2) preparation of doping 0.05wt.% cobaltous acetate colloidal sol
1. it is standby as colloidal sol to adopt graduated cylinder to measure the 1L dehydrated alcohol;
2. the preparation of GTMS sol system: the GTMS of 60mL is slowly poured in an amount of solvent in the stirring, add excessive deionized water then, make the abundant hydrolysis of GTMS;
3. the preparation of TPOZ sol system: the employing methyl aceto acetate is a catalyzer, and at first the methyl aceto acetate with 13mL fully stirs with an amount of solvent, slowly adds the TPOZ of 26.7mL then; To be mixed evenly after, lentamente deionized water is dripped wherein, TPOZ and deionized water mol ratio are 3: 1;
4. above-mentioned two kinds of sol systems place respectively under the room temperature and stir 0.5h;
Mix above-mentioned two kinds of sol systems, stir;
5. the cobaltous acetate of weighing certain mass fully is dissolved in it in proper amount of solvent, pours mixed sols then into, is mixed with the doping cobaltous acetate sol system of 0.05wt.% concentration;
6. add residual solvent under the whipped state in mixed sols, 2h is stirred in sealing.
3) preparation of collosol and gel rete
Concrete preparation process is with embodiment 1.
1) pre-treatment of aluminium and aluminium alloy
Concrete treating processes is with embodiment 1.
2) preparation of doping 0.15wt.% cobaltous acetate colloidal sol
1. it is standby as colloidal sol to adopt graduated cylinder to measure the 1L dehydrated alcohol;
2. the preparation of GTMS sol system: the GTMS of 60mL is slowly poured in an amount of solvent in the stirring, add excessive deionized water then, make the abundant hydrolysis of GTMS;
3. the preparation of TPOZ sol system: the employing methyl aceto acetate is a catalyzer, and at first the methyl aceto acetate with 13mL fully stirs with an amount of solvent, slowly adds the TPOZ of 26.7mL then; To be mixed evenly after, lentamente deionized water is dripped wherein, TPOZ and deionized water mol ratio are 3: 1;
4. above-mentioned two kinds of sol systems place respectively under the room temperature and stir 0.5h;
5. mix above-mentioned two kinds of sol systems, stir;
6. the cobaltous acetate of weighing certain mass fully is dissolved in it in proper amount of solvent, pours mixed sols then into, is mixed with the doping cobaltous acetate sol system of 0.15wt.% concentration;
7. add residual solvent under the whipped state in mixed sols, 2h is stirred in sealing.
3) preparation of collosol and gel rete
Concrete preparation process is with embodiment 1.
1) pre-treatment of aluminium and aluminium alloy
Concrete treating processes is with embodiment 1.
2) preparation of doping 0.5wt.% cobaltous acetate colloidal sol
1. it is standby as colloidal sol to adopt graduated cylinder to measure the 1L dehydrated alcohol;
2. the preparation of GTMS sol system: the GTMS of 60mL is slowly poured in an amount of solvent in the stirring, add excessive deionized water then, make the abundant hydrolysis of GTMS;
3. the preparation of TPOZ sol system: the employing methyl aceto acetate is a catalyzer, and at first the methyl aceto acetate with 13mL fully stirs with an amount of solvent, slowly adds the TPOZ of 26.7mL then; To be mixed evenly after, lentamente deionized water is dripped wherein, TPOZ and deionized water mol ratio are 3: 1;
4. above-mentioned two kinds of sol systems place respectively under the room temperature and stir 0.5h;
5. mix above-mentioned two kinds of sol systems, stir;
6. the cobaltous acetate of weighing certain mass fully is dissolved in it in proper amount of solvent, pours mixed sols then into, is mixed with the doping cobaltous acetate sol system of 0.5wt.% concentration;
7. add residual solvent under the whipped state in mixed sols, 2h is stirred in sealing.
3) preparation of collosol and gel rete
Concrete preparation process is with embodiment 1.
Claims (5)
1. the collosol and gel rete of the cobaltous acetate that mixes, it is characterized in that, the sol system of collosol and gel rete adopts zirconium iso-propoxide and γ-Huan Yangbingyangbingjisanjiayangjiguiwan as presoma, dehydrated alcohol is as solvent, methyl aceto acetate is as catalyzer, and cobaltous acetate is doped in the sol system as additive.
2. the collosol and gel rete of doping cobaltous acetate as claimed in claim 1, it is characterized in that, rete is complete, fine and close, can provide one deck physical barriers for aluminium and aluminium alloy, entering of retardance corrosive medium, thereby suppressed the generation of corrosion reaction on the aluminium alloy, reached the corrosion resisting property that improves aluminium alloy.
3. the collosol and gel rete of doping cobaltous acetate as claimed in claim 1, it is characterized in that, have satisfactory stability and weather resistance, can provide corrosion inhibition for the sol-gel film that is damaged, this corrosion inhibition can slow down even suppress the infringement that corrosive medium causes the metallic surface.
4. a preparation method who prepares as the collosol and gel rete of the described doping cobaltous acetate of right 1-3 is characterized in that, concrete preparation process is as follows:
1) pre-treatment of aluminium and aluminium alloy
1. polishing: adopt sand papering to 800#;
2. flow and wash from the beginning;
3. alkali cleaning: sodium hydroxide 55g/L, 50～60 ℃ of dipping 30s;
4. flow again after the hot water wash and wash from the beginning;
5. bright dipping: chromic acid: 110g/L; Nitric acid: 45g/L; Hydrofluoric acid: 22g/L;
6. flow and wash from the beginning.
2) preparation of colloidal sol
1. it is standby as solvent to adopt graduated cylinder to measure the 1L dehydrated alcohol;
2. the preparation of GTMS sol system: the GTMS of 60mL is slowly poured in an amount of solvent in the stirring, add excessive deionized water then, make the abundant hydrolysis of GTMS;
3. the preparation of TPOZ sol system: the employing methyl aceto acetate is a catalyzer, and at first the methyl aceto acetate with 13mL fully stirs with an amount of solvent, slowly adds the TPOZ of 26.7mL then; To be mixed evenly after, lentamente deionized water is dripped wherein, TPOZ and deionized water mol ratio are 3: 1;
4. above-mentioned two kinds of sol systems place respectively under the room temperature and stir 0.5h;
5. mix above-mentioned two kinds of sol systems, stir;
6. the cobaltous acetate of weighing certain mass fully is dissolved in it in proper amount of solvent, pours mixed sols then into, is mixed with the doping cobaltous acetate sol system of 0.05～0.15wt.% concentration;
7. add residual solvent under the whipped state in mixed sols, 2h is stirred in sealing.
3) preparation of collosol and gel rete
1. dip-coating: will impregnated in 100s in the sol system that configures through the aluminum alloy specimen of pre-treatment, and come out with the VELOCITY EXTRACTION of 1mm/s then;
2. surface drying: in air, place about 10min, place 60 ℃ to place 10min down again;
3. repeat 1. and 2. step the dip-coating 3 times repeatedly of every group of sample;
4. solidify with dry: place 110 ℃ of following 0.5h so that the rete complete drying.
5. as the preparation method of the collosol and gel rete of right 4 described doping cobaltous acetates, it is characterized in that the doping of cobaltous acetate is 0.01～0.5wt.%, preferred doping is 0.05～0.15wt.%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105624659A (en) * | 2014-11-26 | 2016-06-01 | 波音公司 | Corrosion-inhibiting sol-gel coating systems and methods |
| CN107177836A (en) * | 2016-03-11 | 2017-09-19 | 通用汽车环球科技运作有限责任公司 | The coat system and method for cured film are formed on aluminum substrates |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270477A (en) * | 2007-03-16 | 2008-09-24 | 南德铝工业股份有限公司 | Motor vehicle component with sol-gel coating |
| CN101693995A (en) * | 2009-09-08 | 2010-04-14 | 上海波平航空科技有限公司 | Preparation method of aluminum alloy corrosion resistant coating |
-
2010
- 2010-12-14 CN CN 201010586593 patent/CN102080224A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270477A (en) * | 2007-03-16 | 2008-09-24 | 南德铝工业股份有限公司 | Motor vehicle component with sol-gel coating |
| CN101693995A (en) * | 2009-09-08 | 2010-04-14 | 上海波平航空科技有限公司 | Preparation method of aluminum alloy corrosion resistant coating |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105624659A (en) * | 2014-11-26 | 2016-06-01 | 波音公司 | Corrosion-inhibiting sol-gel coating systems and methods |
| CN107177836A (en) * | 2016-03-11 | 2017-09-19 | 通用汽车环球科技运作有限责任公司 | The coat system and method for cured film are formed on aluminum substrates |
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Application publication date: 20110601 |