CN102898885B - Cheap modified paint self-cleaning coating with super-hydrophobicity and preparation method and application thereof - Google Patents
Cheap modified paint self-cleaning coating with super-hydrophobicity and preparation method and application thereof Download PDFInfo
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- CN102898885B CN102898885B CN201210407484.2A CN201210407484A CN102898885B CN 102898885 B CN102898885 B CN 102898885B CN 201210407484 A CN201210407484 A CN 201210407484A CN 102898885 B CN102898885 B CN 102898885B
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Abstract
The invention provides a cheap modified paint self-cleaning coating with super-hydrophobicity and a preparation method thereof, wherein the prepared cheap modified paint self-cleaning coating with the super-hydrophobicity has a nanometer rough surface structure with a coralline or coralline-like surface; the coating is 50-1000 nm in thickness; and a contact angle of water drop on the surface of the coating is 130-150 degrees. The method provided by the invention has the characteristics of simple technology, good repeatability, low cost and unnecessity of high-cost hydrophobic agent for reducing surface free energy. The modified coating, prepared according to the preparation method provided by the invention, can be used for forming films on various base surfaces consisting of construction outer surface, engineering material surface, mining machinery surface and the like, so that the hydrophobicity can be improved, therefore the outdoor service life is prolonged.
Description
Technical field
The present invention relates to paint field, be specifically related to a kind of cheap modification paint automatic cleaning coating with super-hydrophobicity and its preparation method and application.
Adopt the method for adding inorganic particle to increase the roughness of painting layer, thereby increase the hydrophobic performance of painting layer, can increase waterproof and the self-cleaning performance of coating, and therefore extend the life-span of coating.
Background technology
Because water droplet has not wellability to super hydrophobic surface, water droplet can keep spherical on its surface and be very easy to tumble, and the pollutants such as dust is cleared up away tumbling in process.Due to automatically cleaning characteristic, make it have potential using value in the field such as corrosion-resistant coating, drag reduction surface, be therefore subject to the extensive concern from industrial quarters and scientific research circle scientific research personnel.Find by research, realize surface super hydrophobic sexual needs and meet two conditions: 1. this surface has higher surface roughness; 2. this surface has lower surface free energy.According to these two conditions, scientific research personnel prepares the multiple coating with good super-hydrophobicity.As: it is template that the people such as Zhang adopt anodised aluminium, waters the nanometer stick array that casts out polytetrafluoroethylene (PTFE) and SSS compositions of mixtures, and water droplet reaches as high as 171 ° at its surperficial contact angle, and roll angle is less than 5 °.The people such as Jin adopt silica dioxide granule to regulate the pattern of silicon rubber insulator, prepare the silicone rubber coating with micron and nanometer composite structure, make the surface of insulator have super-hydrophobic characteristic, and contact angle can reach 152.5 °.The people such as Kwok adopt modified plasma etching method to carry out etching to the surface of polytetrafluoroethylmaterial material, and for increasing its surperficial roughness, 107 ° when smooth are increased to coarse 153 ° after treatment at its surperficial contact angle to make water droplet.Adopt the prepared surface out of these preparation methods all to there is good super-hydrophobicity, but preparation process relative complex, cost high, be not suitable for large scale application, especially adopt various templates to prepare the method cost of super-hydrophobic coat very high.
Summary of the invention
In order to solve the problem running in super-hydrophobic coat large-scale promotion application process, as preparation process complexity, high in cost of production shortcoming.To realize the large-scale application of super-hydrophobic automatic cleaning coating: as mining machinery, rainproof door and window, outdoor equipment, haulage vehicle etc.
The object of the present invention is to provide a kind of cheap modification paint automatic cleaning coating with super-hydrophobicity.
Another object of the present invention is to provide a kind of preparation method of the cheap modification paint automatic cleaning coating with super-hydrophobicity.
An also object of the present invention is to provide the above-mentioned cheap modification paint automatic cleaning coating with super-hydrophobicity in the application spraying in mining machinery, rainproof door and window, outdoor equipment or haulage vehicle top layer.
In order to realize object of the present invention, the invention provides a kind of cheap modification paint automatic cleaning coating with super-hydrophobicity, it has the nanometer rough surface structure on coralliform or class coralliform surface; The thickness of this coating is 50nm ~ 1000nm; Water droplet is 130 ° ~ 150 ° at its surperficial contact angle.
The present invention also provides a kind of preparation method of the cheap modification paint automatic cleaning coating with super-hydrophobicity, and it comprises the steps:
(1) making ZnO micron and nanometer composite structure particle: in proportion by zinc nitrate hexahydrate solution (Zn(NO
3)
26H
2and hexa solution (C O)
6h
12n
4, HMT) and carry out ultrasonic agitation; Then mixed liquor is placed in after the water bath of 50 ~ 95 DEG C reacts 0.5 ~ 4h and takes out; After room temperature is cooling, outwell supernatant liquor, take out the white ZnO particle that bottom generates, again through the ultrasonic dispersion of ethanol, centrifugal, after ultrasonic procedure is cleaned, be placed in drying box dry, obtain white solid powder and be ZnO micron and nanometer composite structure particle (described ZnO micron and nanometer composite structure particle is the ZnO particle of dandelion shape, its block dimension, 5 microns of left and right, inside has nanometer branch structure);
(2) in proportion step (1) gained ZnO micron and nanometer composite structure particle and paint are scattered in the middle of organic solvent, under heating ultrasonic agitation condition, mixed solution reaction forms the precursor liquid of modification paint automatic cleaning coating;
(3) precursor liquid of described step (2) modification paint automatic cleaning coating is applied to the surface of workpiece, film-forming under field conditions (factors), forms a kind of cheap modification paint automatic cleaning coating with super-hydrophobicity.
Preferably, described in step (1), zinc nitrate hexahydrate solution and hexamethylene tetramine solution have identical concentration, and concentration range is 0.1 ~ 1mol/L, and the volume ratio of the two is 0.5 ~ 2:1.
Preferably, the described ultrasonic power of step (1) is 40 ~ 100W, and ultrasonic time is 10 ~ 60min; The temperature of described stirring is room temperature, and the speed of stirring is 1000 ~ 2000rpm, and the time is 5 ~ 10min; Described centrifugal speed is 1000 ~ 8000rpm, and the centrifugal time is 5 ~ 10min.
Preferably, described in step (2), the mass ratio of micron and nanometer composite structure particle, organic solvent and paint is preferably 0.15 ~ 4.0:0.2 ~ 2.0:1 ~ 16.Described organic solvent is preferably silane coupler, rosin, acetone, various alcohol, aldehyde, ether, benzene, alkane etc.; Wherein silane coupler model has KH-550, KH-560, KH-570, KH-792.
Wherein, the ultrasonic power that heats ultrasonic agitation described in step (2) is 40 ~ 100W, ultrasonic time 10 ~ 60min; The speed stirring is 1000 ~ 2000rpm, and agitating heating temperature is 20 ~ 80 DEG C, and the time of stirring is 30min ~ 4h.
Wherein, described in step (3), being applied to the precursor liquid of the modification paint automatic cleaning coating of surface of the work can be with lifting, spin coating, curtain coating are coated with or spraying process.
Further, the present invention also provides the above-mentioned cheap modification paint automatic cleaning coating with super-hydrophobicity in the application spraying in mining machinery, rainproof door and window, outdoor equipment or haulage vehicle top layer.
Beneficial effect of the present invention:
The present invention adopts ZnO micro-nano composite construction particle as modifier additive, join paint in the middle of mix fully with paint.In conjunction with the roughening of the film forming of ZnO particle own and the hydrophobicity of paint itself, make modified oil lacquer coat possess higher surface roughness and lower surface free energy simultaneously, thereby the more smooth painted surface of hydrophobicity on modified oil lacquer coat surface is greatly increased, water droplet can be become and be reached 150 ° of left and right from 90 ° of left and right of generally painting at its surperficial contact angle, has super-hydrophobic state.
Method technique that the present invention adopts is simple, reproducible, cost is low, reduces the expensive hydrophobic agents (as fluoride reagents) of surface free energy without using.
The present invention gets final product making ZnO micro-nano composite particles with simple chemical liquid deposition, this particle can be realized modification to all paint, for different occasions: as being mixed for glass vehicle window, being mixed for mechanical metal shell etc. with antirust paint with the colored varnish.
The modified coating that the present invention prepares can, in various substrate surface film forming, comprise external surface of buildings, engineering material surface, mining machinery surface etc., can improve its hydrophobicity, increases its outdoor service life.
Brief description of the drawings
Fig. 1 is the surface topography that adopts the modified oil lacquer coat prepared of the inventive method;
Fig. 2 is the state that adopts the modified oil lacquer coat surface water contact that the inventive method prepares.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Adopt JSM6700LV surface sweeping electron microscope to observe the surface topography of modified coating.
Adopt contact angle measurement (Soren, Shanghai Information technology Co., Ltd) to measure at the contact condition on modified oil lacquer coat surface water droplet.
The paint adopting in the present invention can be the various hydrophobic paint that has, as iron red alcohol acid antirust paint GB/T2525, and black alkyd ready mixed paint HG/T2455-93, alkyd varnish GB/T23995, epoxy resin coating etc.The paint using is domestic water chestnut lake board paint.
The power adjustable desktop heating of ultrasonic use Shanghai High Kudos Science Instrument Co., Ltd., the ultrasonic cleaner of model SK2210HP, stirring what use is the Community of Jin Tan County city Jin Cheng Guo Sheng laboratory apparatus 78HW-1 of factory constant temperature blender with magnetic force.What spin-coating method used is the desk-top sol evenning machine of KW-4A type that Chinese Academy of Sciences Microelectronics Institute produces.
Embodiment 1
(1) making ZnO micron and nanometer composite structure particle: getting concentration is 0.5mol/L zinc nitrate hexahydrate solution (Zn(NO
3)
26H
2and 0.5mol/L hexa solution (C O)
6h
12n
4, HMT) and each 200ml carries out ultrasonicly, and ultrasonic power is 80W, and ultrasonic time 30min mixes, and stirs a period of time; Then mixed liquor is placed in after the water bath of 90 DEG C reacts 2h and takes out; After cooling room temperature is cooling, outwell supernatant liquor, take out the white ZnO particle that bottom generates, then through the ultrasonic dispersion of ethanol, ultrasonic power is 80W, ultrasonic time 10min; The centrifugal 5min of 8000rpm, outwell supernatant liquor, after ultrasonic procedure is cleaned, be placed in drying box dry, obtaining white solid powder is ZnO micron and nanometer composite structure particle (described ZnO micron and nanometer composite structure particle is the ZnO particle of dandelion shape, its block dimension, 5 microns of left and right, inside has nanometer branch structure);
(2) preparation of modification paint liquid:
Dandelion shape ZnO micron and nanometer composite structure particle 5g prepared by step (1) and be scattered in respectively (if configuration in a large number in the middle of 100ml KH-550 silane coupler through water chestnut lake board iron oxide red anticorrosive paint (model GB/T2525) 10ml once filtering, constant according to the above ratio), then by the ultrasonic mixing of 80W 30min under two kinds of solution room temperatures, 50 DEG C/1500rpm magnetic agitation 1h, the precursor liquid that forms modified oil lacquer coat is for subsequent use;
(3) modified oil is painted film:
The surface of modification being painted to precursor liquid method of pulling up and is applied to matrix, pull rate is 10cm/min. film-forming under field conditions (factors), forms a kind of modified oil lacquer coat with super-hydrophobicity.
As shown in Figure 1, paint can form on the surface of ZnO particle well coated, and the painted surface of modification simultaneously has higher surface roughness.
As shown in Figure 2, drop reaches 147 ° at the contact angle of common antirust modification painted surface, has super-hydrophobic state.
The paint adopting in the present invention can be the various hydrophobic paint that has.
Embodiment 2
(1) making ZnO micron and nanometer composite structure particle:
Getting 100ml concentration is 0.1mol/L zinc nitrate hexahydrate solution (Zn(NO
3)
26H
2o) and 200ml concentration be 0.1mol/L hexa solution (C
6h
12n
4, HMT) and mix ultrasonic (if configuration is in a large number constant according to the above ratio), ultrasonic power is 40W, ultrasonic time 50min mixes, and stirs a period of time; Then mixed liquor is placed in after the water bath of 95 DEG C reacts 1h and takes out; After cooling room temperature is cooling, outwell supernatant liquor, take out the white ZnO particle that bottom generates, then through the ultrasonic dispersion of ethanol, ultrasonic power is 50W, ultrasonic time 20min; The centrifugal 5min of 5000rpm, outwells supernatant liquor, after ultrasonic procedure is cleaned, is placed in drying box dry, obtains white solid powder and is ZnO micron and nanometer composite structure particle;
(2) preparation of modification paint liquid:
Dandelion shape ZnO micro-nano composite construction particle 2g prepared by embodiment 1 and be scattered in respectively (if configuration in a large number in the middle of 100ml KH-550 silane coupler through the iron oxide red anticorrosive paint 5ml once filtering, constant according to the above ratio), then by the ultrasonic mixing of 40W 30min under two kinds of solution room temperatures, 50 DEG C/2000rpm magnetic agitation 30min, the precursor liquid that forms modified oil lacquer coat is for subsequent use;
(3) modified oil is painted film:
The surface of modification being painted to precursor liquid and is sprayed at matrix, film-forming under field conditions (factors), forms a kind of modified oil lacquer coat with super-hydrophobicity.
The surface contact angle recording with contact angle measurement is 130 °-150 °
Embodiment 3
(1) making ZnO micron and nanometer composite structure particle:
Getting concentration is 0.1mol/L zinc nitrate hexahydrate solution (Zn(NO
3)
26H
2and 0.1mol/L hexa solution (C O)
6h
12n
4, HMT) and each 300ml carries out ultrasonic (if in a large number configuration, constant according to the above ratio), and ultrasonic power is 40W, and ultrasonic time 60min mixes, and stirs a period of time; Then mixed liquor is placed in after the water bath of 50 DEG C reacts 3h and takes out; After cooling room temperature is cooling, outwell supernatant liquor, take out the white ZnO particle that bottom generates, then through the ultrasonic dispersion of ethanol, ultrasonic power is 50W, ultrasonic time 60min; The centrifugal 5min of 6000rpm, outwell supernatant liquor, after ultrasonic procedure is cleaned, be placed in drying box dry, obtaining white solid powder is ZnO micron and nanometer composite structure particle (described ZnO micron and nanometer composite structure particle is the ZnO particle of dandelion shape, its block dimension, 5 microns of left and right, inside has nanometer branch structure);
(2) preparation of modification paint liquid:
Dandelion shape ZnO micro-nano composite construction particle 5g prepared by embodiment 1 and alkyd varnish 5ml are scattered in respectively (if configuration in a large number in the middle of 100ml KH-550 silane coupler, constant according to the above ratio), then by the ultrasonic mixing of 100W 60min under two kinds of solution room temperatures, 50 DEG C/1500rpm magnetic agitation 30min, the precursor liquid that forms modified oil lacquer coat is for subsequent use;
(3) modified oil is painted film:
The surface of modification being painted to precursor liquid curtain coating painting method and is applied to matrix, film-forming under field conditions (factors), forms a kind of modified oil lacquer coat with super-hydrophobicity.
The surface contact angle recording with contact angle measurement is 130 °-150 °
Embodiment 4
(1) making ZnO micron and nanometer composite structure particle:
Getting concentration is 0.2mol/L zinc nitrate hexahydrate solution (Zn(NO
3)
26H
2o) 200ml and 0.2mol/L hexa solution (C
6h
12n
4, HMT) and 100ml carries out ultrasonic (if in a large number configuration, constant according to the above ratio), and ultrasonic power is 80W, and ultrasonic time 30min mixes, and stirs a period of time; Then mixed liquor is placed in after the water bath of 60 DEG C reacts 0.5h and takes out; After cooling room temperature is cooling, outwell supernatant liquor, take out the white ZnO particle that bottom generates, then through the ultrasonic dispersion of ethanol, ultrasonic power is 60W, ultrasonic time 40min; The centrifugal 5min of 2000rpm, outwell supernatant liquor, after ultrasonic procedure is cleaned, be placed in drying box dry, obtaining white solid powder is ZnO micron and nanometer composite structure particle (described ZnO micron and nanometer composite structure particle is the ZnO particle of dandelion shape, its block dimension, 5 microns of left and right, inside has nanometer branch structure);
(2) preparation of modification paint liquid:
Dandelion shape ZnO micro-nano composite construction particle 15g prepared by embodiment 1 and be scattered in respectively (if configuration in a large number in the middle of 100ml acetone soln through the iron oxide red anticorrosive paint 20ml once filtering, constant according to the above ratio), then by the ultrasonic mixing of 60W 60min under two kinds of solution room temperatures, room temperature lower magnetic force stirs (stir speed (S.S.) is 1200rpm) 2h, and the precursor liquid that forms modified oil lacquer coat is for subsequent use;
(3) modified oil is painted film:
The surface of with sol evenning machine, modification being painted to precursor liquid and is spun on the rotating speed of 2000rpm matrix, film-forming under field conditions (factors), forms a kind of modified oil lacquer coat with super-hydrophobicity.
The surface contact angle recording with contact angle measurement is 130 °-150 °
Embodiment 5
(1) making ZnO micron and nanometer composite structure particle:
Getting concentration is 0.1mol/L zinc nitrate hexahydrate solution (Zn(NO
3)
26H
2o) 200ml and 0.1mol/L hexamethylene tetramine solution (C
6h
12n
4, HMT) and 400ml carries out ultrasonicly, and ultrasonic power is 80W, and ultrasonic time 50min mixes, and stirs a period of time; Then mixed liquor is placed in after the water bath of 80 DEG C reacts 4h and takes out; After cooling room temperature is cooling, outwell supernatant liquor, take out the white ZnO particle that bottom generates, then through the ultrasonic dispersion of ethanol, ultrasonic power is 75W, ultrasonic time 50min; The centrifugal 5min of 4000rpm, outwells supernatant liquor, after ultrasonic procedure is cleaned, is placed in drying box dry, obtains white solid powder and is ZnO micron and nanometer composite structure particle;
(2) preparation of modification paint liquid:
Dandelion shape ZnO micro-nano composite construction particle prepared by embodiment 1 is respectively 2g, 5g, the each 50ml of 10g and alkyd varnish is scattered in respectively central (if the configuration in a large number of 200ml rosin, constant according to the above ratio), then by ultrasonic mixing 10min under two kinds of solution room temperatures, room temperature lower magnetic force stirs (stir speed (S.S.) is 1600rpm) 4h, and the precursor liquid that forms modified oil lacquer coat is for subsequent use;
(3) modified oil is painted film:
The surface of with sol evenning machine, modification being painted to precursor liquid and is spun on the rotating speed of 2000rpm matrix, film-forming under field conditions (factors), forms a kind of modified oil lacquer coat with super-hydrophobicity.
The surface contact angle recording with contact angle measurement is 130 °-150 °
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, amendment, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (1)
1. preparation has the method for the cheap modification paint automatic cleaning coating of super-hydrophobicity, and it comprises the steps:
(1) making ZnO micron and nanometer composite structure particle: get concentration and be that 0.5mol/L zinc nitrate hexahydrate solution and the each 200ml of 0.5mol/L hexa solution carry out is ultrasonic, ultrasonic power is 80W, and ultrasonic time 30min mixes, and stirs a period of time; Then mixed liquor is placed in after the water bath of 90 DEG C reacts 2h and takes out; After cooling room temperature is cooling, outwell supernatant liquor, take out the white ZnO particle that bottom generates, then through the ultrasonic dispersion of ethanol, ultrasonic power is 80W, ultrasonic time 10min; The centrifugal 5min of 8000rpm, outwell supernatant liquor, after ultrasonic procedure is cleaned, be placed in drying box dry, obtain white solid powder and be ZnO micron and nanometer composite structure particle, described ZnO micron and nanometer composite structure particle is the ZnO particle of dandelion shape, and its block dimension is 5 microns, inside has nanometer branch structure;
(2) the dandelion shape ZnO micron and nanometer composite structure particle 5g being prepared by step (1) and through once filter water chestnut lake board iron oxide red anticorrosive paint 10ml be scattered in respectively in the middle of 100ml KH-550 silane coupler, then by the ultrasonic mixing of 80W 30min under two kinds of solution room temperatures, 50 DEG C/1500rpm magnetic agitation 1h, the precursor liquid that forms modified oil lacquer coat is for subsequent use;
(3) modification is painted to precursor liquid method of pulling up and be applied to the surface of matrix, pull rate is 10cm/min, and film-forming under field conditions (factors) forms a kind of modified oil lacquer coat with super-hydrophobicity;
Drop reaches 147 ° at the contact angle of common antirust modification painted surface, has super-hydrophobic state.
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| CN104017403B (en) * | 2014-05-28 | 2016-04-27 | 江苏巨珩新材料科技有限公司 | A kind of solvent-free UV coating for surface of aluminum plate and preparation method thereof |
| CN105694732A (en) * | 2016-03-21 | 2016-06-22 | 苏州市湘园特种精细化工有限公司 | Water-proof antibacterial paint |
| CN105670500B (en) * | 2016-04-15 | 2017-12-08 | 南京林业大学 | A kind of preparation method of zinc oxide/Cellulose nanocrystal bluk recombination super-hydrophobic coat |
| 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 |
| CN106590291A (en) * | 2016-12-13 | 2017-04-26 | 天长市银狐漆业有限公司 | Corrosion-resistant expandable graphite water-based ultrathin steel structure fireproof coating and preparation method thereof |
| CN106590299A (en) * | 2016-12-13 | 2017-04-26 | 天长市银狐漆业有限公司 | Heat-resistant expandable graphite water-based ultrathin steel structure fireproof coating and preparation method thereof |
| CN106590298A (en) * | 2016-12-13 | 2017-04-26 | 天长市银狐漆业有限公司 | High-hardness expansible graphite waterborne ultra-thin steel structure fire-retardant coating and preparation method thereof |
| CN113174780B (en) * | 2021-04-26 | 2023-03-17 | 杭州西红柿环保科技有限公司 | Full-degradable dry-pressed aviation lunch box and preparation method thereof |
| CN113522931B (en) * | 2021-07-09 | 2023-03-24 | 浙江工业大学 | Mineral oxidation acid production inhibition method based on in-situ rapid film formation on surface of sulfurized mineral |
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