CN101143989A - Hydrophobic coating and application thereof - Google Patents
Hydrophobic coating and application thereof Download PDFInfo
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- CN101143989A CN101143989A CNA2006100477660A CN200610047766A CN101143989A CN 101143989 A CN101143989 A CN 101143989A CN A2006100477660 A CNA2006100477660 A CN A2006100477660A CN 200610047766 A CN200610047766 A CN 200610047766A CN 101143989 A CN101143989 A CN 101143989A
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Abstract
The invention relates to a metal paint layer, in particular to a preparation and application of the hydrophobic coating, which can be prepared by the following steps: (1) organosilane is heating refluxed in water-alcohol solution to obtain gel precursor; (2) the gel precursor is ultrasonically dispersed with the silicone oil and inorganic nano particles in solvent C1-C4 alcohol for 20 min-1h, followed by heating reflux to get uniform mixed slurry, which is finished paint layer slurry. The invention has simple preparation technology, and low cost, which effectively improve the surface hydrophobicity of metal through hydrophobic treatment of metal material surface, so as to provide an effective way for anticorrosion of material. The invention is applicable for waterproof anticorrosion of metal material, environmental control and life support system for spacecraft and self-cleaning of external wall.
Description
Technical field
The present invention relates to the metallic coating technology, a kind of specifically hydrophobic coating and carry out application in the hydrophobic treatment in the metallic surface.
Background technology
Hydrophobic coating is a kind of coating technology, all is being widely used aspect surface anticorrosion and the waterproof.The typically used of this technology is to be used on the electrode protection of water-soluble electrolyte; Aspect building, the coating of exterior wall requires to have certain hydrophobicity usually, by improving the hydrophobic performance on surface, what can make that the dust on surface and impurity can not be firm sticks to coatingsurface, being easy to be taken away by rainwater, also is the direction that hydrophobic coating is used thereby make the surface have self-cleaning function; Control of the environment of airship and life-support system need provide a basic living condition and suitable Working environment for the spacefarer in addition, this is just to the sealed cabin temperature inside, humidity has certain requirement, thereby material inside is had the requirement that requires and dehumidify of very high water-tight corrosion-proof, also is one of application direction of this hydrophobic coating.
The main component of the surface anticorrosion coating that the past is commonly used is a polymeric film, hydrophobic solid fill, and hydrophobic liquid etc., however because their one-tenth key form is varied, can't realize anticorrosion and the bifunctional protection in aspect such as waterproof to the surface.
Silane is before its remarkable antiseptic property of discovery, and silane is widely used in glass or the high poly-matrix material of ceramic reinforced as tackiness agent.It is reported to have good bonding strength, therefore improved the overall mechanical properties of matrix material greatly through the glass reinforced body of a small amount of silane treatment and the interface of polymer matrix formation.System and comprehensively the research of silane rustless property start from earlier 1990s.Discover that by these silane can be used for the protection of following metal or alloy effectively: aluminium and aluminium alloy, zinc and zinc alloy (comprising steel plate galvanized), iron and iron alloy (comprising plain carbon stool and stainless steel), copper and copper alloy, magnesium and magnesium alloy etc.
Contact angle is a leading indicator weighing the hydrophobic coating performance, and contact angle is big more, and hydrophobic performance is good more.
United States Patent (USP) [US 6743467 B1] has been introduced a kind of hydrophobic material, and it is applied on the coating technology, contact angle has reached more than 150 ℃, yet the preparation method that it adopted has certain requirement to the organosilicon oil viscosity, and our selected organic silicone oil is with low cost, raw material is easy to get, and the metallic surface contact angle of handling through coating has reached 161 ℃.And this coated material is applied to the aperture is 5 microns nickel based metal sheet material, and its contact angle reaches 140 ℃, and not influence of air penetrability.
Summary of the invention
The object of the present invention is to provide a kind of hydrophobic coating and carry out application in the hydrophobic treatment in the metallic surface.The utilization of this material is made by organosilane and silicone oil doping inorganic nano-particle co-processing, utilize the hydrophobic slurries of the feedstock production of nontoxic pollution-free that hydrophobic treatment is carried out in the metallic surface, preparation technology is simple, and cost is low, and effectively raises the hydrophobic ability of metallic surface.
For achieving the above object, employing technical scheme of the present invention is:
A kind of hydrophobic coating can prepare as follows,
1) organosilane reflux in water-alcohol solution is obtained gel precursor;
2) with gel precursor and organic silicone oil, inorganic nano-particle is in solvent C
1-C
4Ultra-sonic dispersion 20min-1h in the alcohol, reflux obtains mixed uniformly slurries then, is the product coating slurries, and the coating slurries are matrix materials of a kind of gel and nanoparticle.
Described organosilane is tetraethoxy or methyl silicate; Organic silicone oil is dimethyl silicone oil or linear body silicone oil; Inorganic nano-particle is nano silicon, nano zirconium dioxide, nano titanium oxide, nano ceric oxide.
The choosing and to be methyl alcohol, ethanol and/or Virahol of alcohol in the water-alcohol solution in the step 1); The volume ratio of silane and water-alcohol solution is 1～2: 2, and the volume ratio of water alcohol is 1 in the water-alcohol solution: 0.5-1.5; Water be deionized water earlier with hydrochloric acid or sulfuric acid adjust pH between 4～6, reflux, return time 12～36 hours;
Step 2) silicone oil, nanoparticle, C in
1-C
4The mass ratio of the organosilane in alcohol and the gel precursor is 0.5～1: 2～5: 80-105: 10; The reflux temperature is 70-90 ℃, return time 12～48 hours; Inorganic nano-particle particle diameter 1-100nm is advisable, and particle diameter is even;
Described coating slurries are used for metal material surface is carried out hydrophobic treatment, and specific operation process is
1) with the slurries that make through ultra-sonic oscillation evenly after, spread upon metal material surface uniformly;
2) metallic substance after will handling promptly obtains hydrophobic coating at metal material surface in 300-410 ℃ of following roasting 5～20min after the cooling.
Should carry out pre-treatment before the metallic substance coating, metallic substance after cleaning surfaces is handled, is soaked in the sodium hydroxide solution of 0.5-2mol/L greater than 10 minutes, 80-105 ℃ of oven dry, standby.
The clean of metallic surface adopts the method for sanding and polishing.
The mode of smearing of slurries can be: dip coating, metallic substance is immersed in the slurries, and at the uniform velocity lift out then; Spin-coating method is immersed in metallic substance in the slurries, controls its speed of rotation and answers 800-1500rpm; Or pick slurries with hairbrush and be applied in metal material surface uniformly.
Described metallic substance comprises all kinds of metal bases, as: nickel, nickelalloy, aluminium, aluminium alloy, zinc, zinc alloy (comprising steel plate galvanized), iron, iron alloy (comprising plain carbon stool and stainless steel), copper, copper alloy, magnesium or magnesium alloy etc.; Porous metal material is as nickel foam etc.
The present invention has following advantage:
1. nontoxic pollution-free.Hydrophobic coating material of the present invention adopts raw material organosilane, organic silicone oil and the inorganic nano-particle of nontoxic pollution-free.Based on the organosilane of siloxane bond, not only nontoxic, harmless, and also the bond energy of siloxane bond is higher, is 443.1kJmol
-1, be prerequisite as necessary anti-certain temperature of coated material and intensity.And the silica bond polarity is very strong, and this is the basis of realizing good combination power with matrix; Widely applicable, the preservative property through the metallic surface that silane treatment is crossed reach the glueability excellence to organic coating.
2. effectively raise the hydrophobic ability of metallic surface.The nanostructure of solid surface plays important effect to super-hydrophobicity, and it can produce very high contact angle; The present invention carries out the microstructure processing by introducing inorganic nano-particle to the surface, reduces the contact surface between water droplet and the solid surface, thereby very easily comes off from solid surface, has realized the hydrophobic treatment to solid surface.
3. technological process is simple.The present invention utilizes organosilane that the gel precursor of hydrophobic performance is arranged by Prepared by Sol Gel Method; Utilize the heat-resisting of silicone oil, the characteristics of ultraviolet-resistant aging and water-tolerant by the blend reflow treatment, are carried out chemical modification to gel precursor.
4. it is convenient to use.The preparation of metallic surface hydrophobic coating is by dip-coating or spin-coating method the surface to be handled, and at last by roasting with paint solidification from the teeth outwards, has effectively shortened the set time of coating.For material anticorrosion provides a kind of valid approach; Be applicable to the water-tight corrosion-proof of metallic substance, the environment control of airship and the application of aspects such as life-support system and exterior wall self-cleaning coating.
Description of drawings
Fig. 1 is the preceding contact angle of the metal plate coating of embodiments of the invention 1 (111 degree) synoptic diagram;
Fig. 2 is the contact angle behind the metal plate coating of specific embodiments of the invention 1 (161.5 degree) synoptic diagram;
Fig. 3 is the preceding contact angle of the metallic cylinder coating of specific embodiments of the invention 2 (85.8 degree) synoptic diagram;
Fig. 4 is the contact angle behind the metallic cylinder coating of specific embodiments of the invention 2 (140 degree) synoptic diagram.
Embodiment
Embodiment 1
Get the hydrochloric acid adjust pH to 4 of 5.4ml deionized water with 1mol/L, with 5g tetraethoxy (TEOS), 5.4ml dehydrated alcohol (EtOH) is mixed, and 97 ℃ of backflows obtained gel precursor in 24 hours.
In gel precursor, add the 3.5g dimethyl silicone oil, 1g nano silicon (particle diameter 7nm), the 50g Virahol mixed the back ultrasonic 120 minutes, the mixed liquid homodisperse of order, 86 ℃ of backflow 48h under stirring condition obtain the coating slurries then, and are ultrasonic, standby.
Getting an area is 2 * 2cm
2The metallic nickel sheet of size, soaks in the sodium hydroxide solution of 1mol/L greater than 10 minutes after the polished finish through polishing, and 90 ℃ of oven dry are standby.
With the slurries that make through sonic oscillation evenly after, be spin-coated on material surface, spin speed is 1000rpm.
Material after handling in 400 ℃ of following roasting 20min, is promptly obtained hydrophobic coating at material surface after the cooling.
Embodiment 2
Get 5.4ml water with hydrochloric acid adjust pH to 6, with 5g tetraethoxy (TEOS), 5.4ml anhydrous methanol (MeOH) is mixed, and 97 ℃ of backflows obtained gel precursor in 24 hours.
Ensuing coating slurry preparation process is with embodiment 1.
Cylindric nickel porous material after cleaning surfaces is handled, is soaked in the sodium hydroxide solution of 1mol/L greater than 10 minutes, 90 ℃ of oven dry, standby.
With the slurries that make through ultra-sonic oscillation evenly after, dip-coating uniformly in 400 ℃ of following roasting 10min, promptly at this material surface obtains hydrophobic coating after the cooling with the material after handling at material surface.
Claims (10)
1. hydrophobic coating is characterized in that: can prepare as follows,
1) organosilane reflux in water-alcohol solution is obtained gel precursor;
2) with gel precursor and organic silicone oil, inorganic nano-particle is in solvent C
1-C
4Ultra-sonic dispersion 20min-1h in the alcohol, reflux obtains mixed uniformly slurries then, is the product coating slurries.
2. according to the described hydrophobic coating of claim 1, it is characterized in that: described organosilane is tetraethoxy or methyl silicate; Organic silicone oil is dimethyl silicone oil or linear body silicone oil; Inorganic nano-particle is nano silicon, nano zirconium dioxide, nano titanium oxide and/or nano ceric oxide.
3. according to the described hydrophobic coating of claim 1, it is characterized in that: the choosing and to be methyl alcohol, ethanol and/or Virahol of alcohol in the water-alcohol solution in the described step 1); The volume ratio of silane and water-alcohol solution is 1～2: 2, and the volume ratio of water alcohol is 1 in the water-alcohol solution: 0.5-1.5; Water be deionized water earlier with hydrochloric acid or sulfuric acid adjust pH between 4～6, reflux, return time 12～36 hours.
4. according to the described hydrophobic coating of claim 1, it is characterized in that: silicone oil, nanoparticle, C described step 2)
1-C
4The mass ratio of the organosilane in alcohol and the gel precursor is 0.5～1: 2～5: 80-105: 10; The reflux temperature is 70-90 ℃, return time 12～48 hours.
5. according to the described hydrophobic coating of claim 1, it is characterized in that: described inorganic nano-particle particle diameter 1-100nm is advisable, and particle diameter is even.
6. the application of the described hydrophobic coating of claim 1 is characterized in that: described coating slurries are used for metal material surface is carried out hydrophobic treatment, and specific operation process is
1) with the slurries that make through ultra-sonic oscillation evenly after, spread upon metal material surface uniformly;
2) metallic substance after will handling promptly obtains hydrophobic coating at metal material surface in 300-410 ℃ of following roasting 5～20min after the cooling.
7. according to the application of the described hydrophobic coating of claim 6, it is characterized in that: should carry out pre-treatment before the described metallic substance coating, metallic substance after cleaning surfaces is handled, is soaked in the sodium hydroxide solution of 0.5-2mol/L greater than 10 minutes, 80-105 ℃ of oven dry, standby.
8. according to the application of the described hydrophobic coating of claim 7, it is characterized in that: the clean of described metallic surface adopts the method for sanding and polishing.
9. according to the application of the described hydrophobic coating of claim 6, it is characterized in that: the mode of smearing of described slurries can be: dip coating, metallic substance is immersed in the slurries, and at the uniform velocity lift out then; Spin-coating method is immersed in metallic substance in the slurries, controls its speed of rotation and answers 800-1500rpm; Or pick slurries with hairbrush and be applied in metal material surface uniformly.
10. according to the application of the described hydrophobic coating of claim 6, it is characterized in that: described metallic substance nickel, nickelalloy, aluminium, aluminium alloy, zinc, zinc alloy, iron, iron alloy, copper, copper alloy, magnesium or magnesium alloy.
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| CNA2006100477660A CN101143989A (en) | 2006-09-15 | 2006-09-15 | Hydrophobic coating and application thereof |
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|---|---|---|---|
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| CN102002319A (en) * | 2010-12-22 | 2011-04-06 | 复旦大学 | High-temperature-resistant superhydrophobic surface and preparation method thereof |
| CN102241944A (en) * | 2010-05-11 | 2011-11-16 | 林坤 | Waterproofing agent for floor rabbet |
| CN102453465A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Adhesive super-hydrophobic material and preparation method thereof |
| CN102553813A (en) * | 2012-02-17 | 2012-07-11 | 天津大学 | Sol-gel method for preparing micro/nano titanium dioxide and lyophobic film thereof on metal surfaces |
| CN103184007A (en) * | 2013-03-15 | 2013-07-03 | 佛山市登宇洁具有限公司 | Easy-to-clean hydrophobic coating |
| CN103421423A (en) * | 2013-08-01 | 2013-12-04 | 华南理工大学 | Method for preparing high-temperature-resistant super-hydrophobic coating in situ |
| CN103865379A (en) * | 2012-12-11 | 2014-06-18 | 深圳富泰宏精密工业有限公司 | Polydimethylsiloxane sol, method for surface treatment of metal matrix by using polydimethylsiloxane sol, and product obtained through method |
| CN104987833A (en) * | 2015-05-19 | 2015-10-21 | 东莞市兴族实业有限公司 | Reactive nano-silica waterproof liquid for electronic products, and waterproof method thereof |
| CN106046980A (en) * | 2016-06-28 | 2016-10-26 | 山东科技大学 | Surface treatment and anti-fouling method for stainless steel material |
| WO2016186570A1 (en) * | 2015-05-19 | 2016-11-24 | Ah Eng Siaw | A method of optimising energy usage |
| WO2016186569A1 (en) * | 2015-05-19 | 2016-11-24 | Ah Eng Siaw | A composition for optimising energy usage |
| CN107245255A (en) * | 2017-07-21 | 2017-10-13 | 南通天驰环保科技有限公司 | A kind of dirt-proof nanometer coating liquid easy to clean and its preparation method and application |
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| CN102241944A (en) * | 2010-05-11 | 2011-11-16 | 林坤 | Waterproofing agent for floor rabbet |
| CN102453465A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Adhesive super-hydrophobic material and preparation method thereof |
| CN102453465B (en) * | 2010-10-27 | 2014-09-03 | 中国科学院大连化学物理研究所 | Adhesive super-hydrophobic material and preparation method thereof |
| CN102002319B (en) * | 2010-12-22 | 2013-10-16 | 复旦大学 | High-temperature-resistant superhydrophobic surface and preparation method thereof |
| CN102002319A (en) * | 2010-12-22 | 2011-04-06 | 复旦大学 | High-temperature-resistant superhydrophobic surface and preparation method thereof |
| CN102553813A (en) * | 2012-02-17 | 2012-07-11 | 天津大学 | Sol-gel method for preparing micro/nano titanium dioxide and lyophobic film thereof on metal surfaces |
| CN102553813B (en) * | 2012-02-17 | 2013-10-30 | 天津大学 | Sol-gel method for preparing micro/nano titanium dioxide and lyophobic film thereof on metal surfaces |
| CN103865379A (en) * | 2012-12-11 | 2014-06-18 | 深圳富泰宏精密工业有限公司 | Polydimethylsiloxane sol, method for surface treatment of metal matrix by using polydimethylsiloxane sol, and product obtained through method |
| CN103184007B (en) * | 2013-03-15 | 2016-06-29 | 佛山市登宇洁具有限公司 | A kind of easy clean hydrophobic coating |
| CN103184007A (en) * | 2013-03-15 | 2013-07-03 | 佛山市登宇洁具有限公司 | Easy-to-clean hydrophobic coating |
| CN103421423A (en) * | 2013-08-01 | 2013-12-04 | 华南理工大学 | Method for preparing high-temperature-resistant super-hydrophobic coating in situ |
| CN103421423B (en) * | 2013-08-01 | 2015-10-28 | 华南理工大学 | A kind of in-situ preparation method of resistant to elevated temperatures super-hydrophobic coat |
| CN104987833A (en) * | 2015-05-19 | 2015-10-21 | 东莞市兴族实业有限公司 | Reactive nano-silica waterproof liquid for electronic products, and waterproof method thereof |
| WO2016186570A1 (en) * | 2015-05-19 | 2016-11-24 | Ah Eng Siaw | A method of optimising energy usage |
| WO2016186569A1 (en) * | 2015-05-19 | 2016-11-24 | Ah Eng Siaw | A composition for optimising energy usage |
| CN106046980A (en) * | 2016-06-28 | 2016-10-26 | 山东科技大学 | Surface treatment and anti-fouling method for stainless steel material |
| CN106046980B (en) * | 2016-06-28 | 2018-02-13 | 山东科技大学 | A kind of surface of stainless steel processing and anti-fouling method |
| CN107245255A (en) * | 2017-07-21 | 2017-10-13 | 南通天驰环保科技有限公司 | A kind of dirt-proof nanometer coating liquid easy to clean and its preparation method and application |
| CN108000654A (en) * | 2017-11-27 | 2018-05-08 | 北京林业大学 | Nanometer Ag-TiO2Wood mould antiseptic and its preparation method and application |
| CN109401616A (en) * | 2018-11-06 | 2019-03-01 | 深圳市溯元科技有限公司 | A kind of anti-doodling paint and preparation method thereof |
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