CN105295707A - Corrosion-preventive and rust-resistant sol for aluminum alloy and preparation method thereof - Google Patents
Corrosion-preventive and rust-resistant sol for aluminum alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses corrosion-preventive and rust-resistant sol for aluminum alloy. The corrosion-preventive and rust-resistant sol is prepared from, by weight, 2-3 parts of methyl 4-hydroxybenzoate, 1-2 parts of butylnaphtalenesulfonic acid sodium salt, 10-12 parts of nano-titanium dioxide, 0.8-1 part of stearic acid, 0.2-0.4 part of sodium dodecyl benzene sulfonate, 10-18 parts of dodecafluoroheptyl-propyl-trimethoxysilane, 20-30 parts of hydrogen-containing silicone oil, 0.7-1 part of 25%-28% ammonium hydroxide, 1-2 parts of silane coupling agent KH560, 90-100 parts of 2,3-dimethylaniline, 0.6-1 part of ammonium persulfate, 3-4 parts of hydroxystearic acid, 0.6 part of polybenzimidazole, 2-3 parts of diethylene glycol, 0.3-1 part of tallowseed oil and 0.1-0.2 part of dibutyl maleate. The coating film has good corrosion-preventive and rust-resistant performance, high in water resistance and acid-base resistance, good in bonding property with a base material, and high and lasting in protection.
Description
Technical field
The present invention relates to technical field of aluminum alloy technology, particularly relate to a kind of corrosive protection of aluminium alloy rust-proofing colloidal sol and preparation method thereof.
Background technology
As everyone knows, contact angle (CA) is greater than 150 ° and the surface that roll angle (SA) is less than 10 ° is called super hydrophobic surface by us.In recent years, super hydrophobic material is widely used in fundamental research, daily life and industrial production with the performance of its uniqueness, can be used for the fields such as Metal surface anti-corrosion, fluid drag-reduction, waterproof, antifouling and automatically cleaning, organic-inorganic nanocomposite is as the field of emerging emergence, in super-hydrophobic composite organic-inorganic material system, critical positions is occupied with its superior performance, main with organic and inorganic thing for raw material, adopt proper method to make it to be composited by chemical bond within the scope of micro-/ nano.Wherein, inorganic nano-particle Chang Zuowei packing material, obtains micro-/ nano secondary structure with organism compound, gives matrix material superhydrophobic property;
Metal is under the effect of surrounding medium (especially water and air), and the destruction produced due to chemical reaction, electrochemical reaction or physical dissolution is exactly corrosion of metal, is the inverse process of the spontaneous a kind of metallurgy carried out silently.The industrial media such as the physical environments such as air, soil, seawater and microorganism and acid, alkali, salt, combustion gas all likely cause corrosion of metal.The harm that metallic corrosion brings, throughout the every field of national economy, comprises chemical industry, the energy, machinery, aerospace, information, agricultural, ocean exploitation and Infrastructure etc.As long as use the place of metallic substance, all more or less there is etching problem.The etching problem of metallic substance and study effective aseptic technic oneself becomes the problem of can not ignore in current Materials Science and Engineering field;
Polyaniline has cheaper starting materials and is easy to get, synthesizes the feature such as simple and be counted as the high-performance impregnating material of a new generation.After the polyaniline film proposing first to adopt electrochemical method to prepare from DeBerry in 1985 has passivation on stainless steel surface, polyaniline has become a new focus in the research and development in anticorrosion.Although the anticorrosion mechanism of polyaniline is not also completely understood, the antiseptic property of the excellence that polyaniline shows is mathematical, and therefore, people still proceed further investigation to it.At present, the research for polyaniline is mainly divided into two aspects: one is on existing Research foundation, continues p-poly-phenyl amine anticorrosion mechanism and carries out comparatively deep research and exploitation; Two is the barrier propterties carrying out to improve further polyaniline coating by all means.
Summary of the invention
The object of the invention is exactly the defect in order to make up prior art, provides a kind of corrosive protection of aluminium alloy rust-proofing colloidal sol and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of corrosive protection of aluminium alloy rust-proofing colloidal sol, it is made up of the raw material of following weight parts:
Methyl p-hydroxybenzoate 2-3, sodium butylnaphthalenesulfonate 1-2, nano titanium oxide 10-12, stearic acid 0.8-1, Sodium dodecylbenzene sulfonate 0.2-0.4, ten difluoro heptyl propyl trimethoxy silicane 10-18, ammoniacal liquor 0.7-1, the silane coupling agent KH5601-2 of containing hydrogen silicone oil 20-30,25-28%, 23 dimethyl aniline 90-100, ammonium persulphate 0.6-1, oxystearic acid 3-4, polybenzimidazole 0.6-glycol ether 2-3, Chinese vegetable tallow 0.3-1, dibutyl maleinate 0.1-0.2;
A preparation method for described corrosive protection of aluminium alloy rust-proofing colloidal sol, comprises the following steps:
(1) join in dehydrated alcohol by above-mentioned stearic acid, stirring and dissolving, described dehydrated alcohol and stearic envelope-bulk to weight ratio are 25-30:1;
(2) above-mentioned nano titanium oxide is joined its weight 10-12 doubly, in the ethanolic soln of 60-65%, magnetic agitation is even, adds above-mentioned stearic ethanolic soln, magnetic agitation 3-4 hour, dry at 120-125 DEG C, grinding, obtains stearic acid modified titanium dioxide;
(3) by above-mentioned oxystearic acid, glycol ether mixing, insulated and stirred 20-30 minute at 70-80 DEG C, adds above-mentioned Chinese vegetable tallow, be stirred to normal temperature, mix with the 4-6% of above-mentioned 23 dimethyl aniline weight, 70-100 rev/min is stirred 10-20 minute, obtains premix monomer;
(4) 40-50% of above-mentioned Sodium dodecylbenzene sulfonate weight is got, join in 180-200 times of deionized water, stir, add ten difluoro heptyl propyl trimethoxy silicanes, containing hydrogen silicone oil, 1000-1200 rev/min is stirred 2-3 hour, drip the Karstedt catalyzer of above-mentioned system weight 1-2%, stirring reaction 1-2 hour, obtains fluorinated silicone oil;
(5) remaining Sodium dodecylbenzene sulfonate is got, join in its weight 70-100 times deionized water, stir, drip the ammoniacal liquor of above-mentioned 25-28%, remaining 2 are added after dropwising, 3-xylidine, stir, raised temperature is 50-60 DEG C, add above-mentioned stearic acid modified titanium dioxide, insulated and stirred 10-20 minute, reduction temperature is 30-35 DEG C, add ammonium persulphate, insulated and stirred 9-10 hour, add above-mentioned premix monomer, continue insulated and stirred 1-2 hour, suction filtration, vacuum-drying 30-40 minute at 90-100 DEG C, obtain polymer modification titanium dioxide,
(6) joined in 2-3 times of dehydrated alcohol by above-mentioned methyl p-hydroxybenzoate, add above-mentioned polybenzimidazole, insulated and stirred 10-17 minute at 60-76 DEG C, obtains corrosion inhibiting solution;
(7) get above-mentioned sodium butylnaphthalenesulfonate, join in 3-4 times of deionized water, mix, stir with above-mentioned corrosion inhibiting solution, add silane coupling agent KH560,100-200 rev/min is stirred 4-6 minute, obtains solution of silane:
(8) join in fluorinated silicone oil by above-mentioned polymer modification titanium dioxide, stir, add solution of silane, stir, adjustment PH is 5-6, insulated and stirred 3-4 hour at 50-60 DEG C, adds each raw material of residue, stirs, obtain composite modified colloidal sol.
Described a kind of corrosive protection of aluminium alloy lift colloidal sol, the using method of this colloidal sol is:
Be immersed in by aluminium flake clean for surface treatment in this composite modified colloidal sol, carry out Best-Effort request plated film, namely repeatable operation obtains certain thickness uniform thin film, under being then placed in room temperature after dry 20-30min, under 125-130 DEG C of condition, cures 25-30min.
Advantage of the present invention is:
The film of gel formation of the present invention has good water resisting property:
Stearic acid contain a large amount of-COOH group, dehydration reaction can be there is with surface of inorganic particles-OH, also hydrophobicity-CH3 group can be introduced for TiO2, but modified TiO2 is poor at body surface sticking power, easy generation obscission, containing hydrogen silicone oil has good chemical stability and high hydrophobicity energy, can interact with inorganic particulate and form abundant microtexture, ten difluoro heptyl propyl trimethoxy silicanes contain hydrophobicity-CH3 and hydrolyzable-OCH3, it is utilized to fluoridize containing hydrogen silicone oil, containing hydrogen silicone oil generation dehydrogenation coupling reaction can be made, more excellent mechanical property is possessed under crosslinked action, make compound coating more stable, in addition, the hydrophobic methyl introduced also can increase the hydrophobic effect of coating,
The film of gel formation of the present invention has good non-corrosibility:
Micro/nano structure of the present invention has effectively intercepted air in water and has contacted with the direct of aluminium flake substrate, and the amount of oxygen making aluminium flake surface participate in reaction reduces, thus slow down the generation of aluminium flake surface film oxide; On the other hand, the reticulated structure formed by Si-O had in compound coating is combined with aluminium flake intimate surface, the fluoroalkyl of hydrophobic then points to corrodibility NaCl solution one end, in addition, the modifying titanium dioxide of compound coating surface compact possesses abundant surface microstructure and has low surface energy, and this plays a key effect to the protection against corrosion of coating;
The present invention introduces polyaniline in gel, make the reduction reaction of oxygen from the metal/corrosive medium interfacial migration of routine to polymkeric substance/corrosive medium interface, decrease the generation at metal/corrosive medium surface OH-, prevent the rising of metallic surface pH, serve good corrosion mitigating effect, effectively prevent the degraded of coating, peel off;
Film of the present invention has good anticorrosion rust-resisting property, and water-fast, resistance to acids and bases is strong, good with the cohesiveness of base material, and protectiveness is strong and lasting.
Embodiment
A kind of corrosive protection of aluminium alloy rust-proofing colloidal sol, it is made up of the raw material of following weight parts:
Methyl p-hydroxybenzoate 2, sodium butylnaphthalenesulfonate 1, nano titanium oxide 10, stearic acid 0.8, Sodium dodecylbenzene sulfonate 0.2, ten difluoro heptyl propyl trimethoxy silicane 10, the ammoniacal liquor 0.7 of containing hydrogen silicone oil 20,25%, silane coupling agent KH5601,2,3 xylidines 90, ammonium persulphate 0.6, oxystearic acid 3, polybenzimidazole 0.6 glycol ether 2, Chinese vegetable tallow 0.3, dibutyl maleinate 0.1;
A preparation method for described corrosive protection of aluminium alloy rust-proofing colloidal sol, comprises the following steps:
(1) join in dehydrated alcohol by above-mentioned stearic acid, stirring and dissolving, described dehydrated alcohol and stearic envelope-bulk to weight ratio are 25:1;
(2) above-mentioned nano titanium oxide is joined its weight 10 times, 60% ethanolic soln in, magnetic agitation is even, adds above-mentioned stearic ethanolic soln, magnetic agitation 3 hours, dries at 120 DEG C, and grinding, obtains stearic acid modified titanium dioxide;
(3) by above-mentioned oxystearic acid, glycol ether mixing, at 70 DEG C, insulated and stirred 20 minutes, adds above-mentioned Chinese vegetable tallow, is stirred to normal temperature, with above-mentioned 2, and 4% mixing of 3 xylidine weight, 70 revs/min are stirred 10 minutes, obtain premix monomer;
(4) 40% of above-mentioned Sodium dodecylbenzene sulfonate weight is got, join in 180 times of deionized waters, stir, add ten difluoro heptyl propyl trimethoxy silicanes, containing hydrogen silicone oil, 1000 revs/min are stirred 2 hours, drip the Karstedt catalyzer of above-mentioned system weight 1%, stirring reaction 1 hour, obtains fluorinated silicone oil;
(5) remaining Sodium dodecylbenzene sulfonate is got, join in its weight 70 times of deionized waters, stir, drip the ammoniacal liquor of above-mentioned 25%, after dropwising, add remaining 2,3 xylidines, stir, raised temperature is 50 DEG C, adds above-mentioned stearic acid modified titanium dioxide, insulated and stirred 10 minutes, reducing temperature is 30 DEG C, add ammonium persulphate, insulated and stirred 9 hours, add above-mentioned premix monomer, continue insulated and stirred 1 hour, suction filtration, at 90 DEG C, vacuum-drying 30 minutes, obtains polymer modification titanium dioxide;
(6) joined in 2 times of dehydrated alcohols by above-mentioned methyl p-hydroxybenzoate, add above-mentioned polybenzimidazole, at 60 DEG C, insulated and stirred 10 minutes, obtains corrosion inhibiting solution;
(7) get above-mentioned sodium butylnaphthalenesulfonate, join in 3 times of deionized waters, mix, stir with above-mentioned corrosion inhibiting solution, add silane coupling agent KH560,100 revs/min are stirred 4 minutes, obtain solution of silane:
(8) above-mentioned polymer modification titanium dioxide is joined in fluorinated silicone oil, stir, add solution of silane, stir, regulate PH to be 5, insulated and stirred 3 hours at 50 DEG C, add each raw material of residue, stir, obtain composite modified colloidal sol.
Described a kind of corrosive protection of aluminium alloy lift colloidal sol, the using method of this colloidal sol is:
Be immersed in by aluminium flake clean for surface treatment in this composite modified colloidal sol, carry out Best-Effort request plated film, namely repeatable operation obtains certain thickness uniform thin film, under being then placed in room temperature after dry 20min, under 125 DEG C of conditions, cures 25min.
Performance test:
Water-intake rate: according to the method described above surface treatment agent of the present invention is coated on the aluminum alloy surface being of a size of 5cm × 6cm, soaks 48h in the deionized water of 25 DEG C, and recording water-intake rate is 9.3%;
Sticking power: 1 grade;
Erosion resistance: neutral salt spray test 72 hours, be corroded area 2.0%;
Hardness: 3H.
Claims (3)
1. a corrosive protection of aluminium alloy rust-proofing colloidal sol, is characterized in that, it is made up of the raw material of following weight parts:
Methyl p-hydroxybenzoate 2-3, sodium butylnaphthalenesulfonate 1-2, nano titanium oxide 10-12, stearic acid 0.8-1, Sodium dodecylbenzene sulfonate 0.2-0.4, ten difluoro heptyl propyl trimethoxy silicane 10-18, the ammoniacal liquor 0.7-1 of containing hydrogen silicone oil 20-30,25-28%, silane coupling agent KH5601-2,23 dimethyl aniline 90-100, ammonium persulphate 0.6-1, oxystearic acid 3-4, polybenzimidazole 0.6-1, glycol ether 2-3, Chinese vegetable tallow 0.3-1, dibutyl maleinate 0.1-0.2.
2. a preparation method for corrosive protection of aluminium alloy rust-proofing colloidal sol as claimed in claim 1, is characterized in that, comprise the following steps:
(1) join in dehydrated alcohol by above-mentioned stearic acid, stirring and dissolving, described dehydrated alcohol and stearic envelope-bulk to weight ratio are 25-30:1;
(2) above-mentioned nano titanium oxide is joined its weight 10-12 doubly, in the ethanolic soln of 60-65%, magnetic agitation is even, adds above-mentioned stearic ethanolic soln, magnetic agitation 3-4 hour, dry at 120-125 DEG C, grinding, obtains stearic acid modified titanium dioxide;
(3) by above-mentioned oxystearic acid, glycol ether mixing, insulated and stirred 20-30 minute at 70-80 DEG C, adds above-mentioned Chinese vegetable tallow, be stirred to normal temperature, mix with the 4-6% of above-mentioned 23 dimethyl aniline weight, 70-100 rev/min is stirred 10-20 minute, obtains premix monomer;
(4) 40-50% of above-mentioned Sodium dodecylbenzene sulfonate weight is got, join in 180-200 times of deionized water, stir, add ten difluoro heptyl propyl trimethoxy silicanes, containing hydrogen silicone oil, 1000-1200 rev/min is stirred 2-3 hour, drip the Karstedt catalyzer of above-mentioned system weight 1-2%, stirring reaction 1-2 hour, obtains fluorinated silicone oil;
(5) remaining Sodium dodecylbenzene sulfonate is got, join in its weight 70-100 times deionized water, stir, drip the ammoniacal liquor of above-mentioned 25-28%, remaining 2 are added after dropwising, 3-xylidine, stir, raised temperature is 50-60 DEG C, add above-mentioned stearic acid modified titanium dioxide, insulated and stirred 10-20 minute, reduction temperature is 30-35 DEG C, add ammonium persulphate, insulated and stirred 9-10 hour, add above-mentioned premix monomer, continue insulated and stirred 1-2 hour, suction filtration, vacuum-drying 30-40 minute at 90-100 DEG C, obtain polymer modification titanium dioxide,
(6) joined in 2-3 times of dehydrated alcohol by above-mentioned methyl p-hydroxybenzoate, add above-mentioned polybenzimidazole, insulated and stirred 10-17 minute at 60-76 DEG C, obtains corrosion inhibiting solution;
(7) get above-mentioned sodium butylnaphthalenesulfonate, join in 3-4 times of deionized water, mix, stir with above-mentioned corrosion inhibiting solution, add silane coupling agent KH560,100-200 rev/min is stirred 4-6 minute, obtains solution of silane:
(8) join in fluorinated silicone oil by above-mentioned polymer modification titanium dioxide, stir, add solution of silane, stir, adjustment PH is 5-6, insulated and stirred 3-4 hour at 50-60 DEG C, adds each raw material of residue, stirs, obtain composite modified colloidal sol.
3. a kind of corrosive protection of aluminium alloy lift colloidal sol according to claim 1, it is characterized in that, the using method of this colloidal sol is:
Be immersed in by aluminium flake clean for surface treatment in this composite modified colloidal sol, carry out Best-Effort request plated film, namely repeatable operation obtains certain thickness uniform thin film, under being then placed in room temperature after dry 20-30min, under 125-130 DEG C of condition, cures 25-30min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250805A (en) * | 2017-12-05 | 2018-07-06 | 安徽工程大学 | A kind of microelectronic device surface acid-proof coating formula and preparation method thereof |
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| CN101088606A (en) * | 2006-06-12 | 2007-12-19 | 中国科学院理化技术研究所 | Prepn process of nanometer composite titania/silica photocatalyst sol and transparent photocatalyzing film |
| CN102453429A (en) * | 2010-10-26 | 2012-05-16 | 浙江大学 | Preparation method for nano-TiO2/organic silicon metal anti-corrosion coating |
| CN102516477A (en) * | 2011-11-23 | 2012-06-27 | 华南理工大学 | Nano titanium dioxide/ acrylate composite emulsion and preparation method thereof |
| CN103224719A (en) * | 2013-02-04 | 2013-07-31 | 湖北大学 | Fluorosilicone material for super-hydrophobic coating and its preparation method and use method |
| CN104448960A (en) * | 2014-12-15 | 2015-03-25 | 广西科技大学 | Preparation method of nano titanium dioxide/zinc oxide super-hydrophobic compound coating |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088606A (en) * | 2006-06-12 | 2007-12-19 | 中国科学院理化技术研究所 | Prepn process of nanometer composite titania/silica photocatalyst sol and transparent photocatalyzing film |
| CN102453429A (en) * | 2010-10-26 | 2012-05-16 | 浙江大学 | Preparation method for nano-TiO2/organic silicon metal anti-corrosion coating |
| CN102516477A (en) * | 2011-11-23 | 2012-06-27 | 华南理工大学 | Nano titanium dioxide/ acrylate composite emulsion and preparation method thereof |
| CN103224719A (en) * | 2013-02-04 | 2013-07-31 | 湖北大学 | Fluorosilicone material for super-hydrophobic coating and its preparation method and use method |
| CN104448960A (en) * | 2014-12-15 | 2015-03-25 | 广西科技大学 | Preparation method of nano titanium dioxide/zinc oxide super-hydrophobic compound coating |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108250805A (en) * | 2017-12-05 | 2018-07-06 | 安徽工程大学 | A kind of microelectronic device surface acid-proof coating formula and preparation method thereof |
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Application publication date: 20160203 |