CN104629620A - Method for preparing superhydrophobic anti-icing paint and coating - Google Patents
Method for preparing superhydrophobic anti-icing paint and coating Download PDFInfo
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Abstract
The invention discloses a method for preparing a superhydrophobic anti-icing paint and coating. The preparation raw materials comprise a silane coupling agent, silica sol, a short fluorocarbon chain-substituted silane coupling agent and water. The preparation method comprises the following steps: under the protection of nitrogen, uniformly mixing the silane coupling agent, the silica sol, and the short chain fluorocarbon-substituted silane coupling agent, reacting at a temperature of 40 to 80 DEG C while dropwisely adding the water, continuously reacting for 3-5h after the dropwise addition is finished, thus preparing the superhydrophobic anti-icing paint; continuously coating the paint on the surface of a substrate through a dip coating method; performing heat treatment to obtain the coating with lasting low surface energy and superhydrophobic property. The preparation method further comprises the step of prior to the paint coating, soaking the surface of the substrate in alkaline anhydrous ethanol with pH of 9-11 for 3 to 7 days. The coating prepared by the invention exhibits a good anti-icing performance, and can be used in transmission and communication equipment, railways, aviation and other fields. The method provided by the invention has the advantages of simple process, easiness in operation and environmental friendliness.
Description
Technical field
The present invention is specifically related to the preparation method of a kind of super-hydrophobic ice-covering-proof coating and coating, belongs to material surface engineering technolog field.
Background technology
At the beginning of 2008, an ice disaster attacks southern china dozens of provinces and regions, cause transmit electricity signal equipment, transportation by railroad facility of southern most area to be inflicted heavy losses on, people life receives serious impact, and the direct economic loss caused because of disaster reaches 111,100,000,000 yuan.Icing is the very general phenomenon of nature, works air icing, as aircraft wing and shell freezes, the icing of the deck icing of wire icing, warship, mast and antenna, railroad track icing etc., are all common spontaneous phenomenons.But can make when this phenomenon is serious that transmission of electricity communication link interrupts, transportation by railroad is obstructed, and brings inconvenience, even life-threatening property safety to people's productive life.Therefore, ice-covering-proof technical study is significant.
Current anti-icing technical study mainly contains that Four types ie in solution is anti-icing, mechanical deicing, heat energy is anti-icing and coating is anti-icing.Anti-icing because the energy consumption of its floating coat is little, applied widely and belong to active protection, and therefore compare other three kinds of methods, coating is anti-icing is a kind of very desirable anti-icing method.
Hydrophobic material is the main flow of ice-covering-proof coating research.According to Young ' s equation [Philosophical Transactions of the Royal Society of London, 1805,95:65-87], the solid surface of static contact angle θ >90 ° of water can not be flooded profit, is hydrophobic surface; When θ >150 ° and Structure deformation angle θ
rduring <10 °, this surface is super hydrophobic surface [LANGMUIR, 2007,23 (4): 2169-2174].The static contact angle that super hydrophobic surface is larger is conducive to increasing the potential barrier of water condensation, extends freezing time, and less roll angle is conducive to drop and tumbles rapidly and do not remain.And receive micro-coarse structured had air cushion due to super hydrophobic surface, drop is made to form solid-liquid-gas three-phase coexistence interface at super hydrophobic surface, have good heat insulating function with the air cushion of liquid comes into contact, when on the interface that drop drips to low temperature, icing rate reduces greatly.Therefore, current super-hydrophobic ice-covering-proof coating has become most active research theme and hot issue.
In the research of super-hydrophobic ice-covering-proof coating, organic fluorine material is because have superior low surface energy, and be widely used [SCI, 2013(03): 703-707] in hydrophobic anti-icing paint.As: CN102660182A has invented a kind of special construction of nanoparticle that utilizes and has combined with the fluorine-contaninig polyacrylate multipolymer of low surface energy, obtain super-hydrophobic, low adhesion, receive micro-coarse structured ice-covering-proof material uniformly, this coated material obtains good ice-covering-proof effect; For another example CN102443326A discloses one and utilizes urn glass powder to be combined with tetrafluoroethylene to obtain hydrophobic performance, thus preparation has the coating of better anti-icing performance.But the organic fluorine material being the fluorocarbon chain structure of C>=8 that these ice-covering-proof coatings utilize, the organic materials of this long fluorocarbon chain structure greatly, not easily decomposes environmental hazard and degradation production has long-term harm to environment.
The current super-hydrophobic ice-covering-proof coating of bibliographical information or the preparation technology of coating in addition, most complicated multistep, coating process requires harsh, not easily actual widespread adoption.
Summary of the invention
For overcoming the problem of prior art, the object of the present invention is to provide a kind of environmental friendliness and preparation technology is simple, the super-hydrophobic ice-covering-proof coating of easy handling and the preparation method of coating.
The invention provides a kind of preparation method of super-hydrophobic ice-covering-proof coating, its preparation process is: under nitrogen protection, the silane coupling agent that silane coupling agent, silicon sol, short fluorocarbon chain replace is mixed, 40 DEG C ~ 80 DEG C following coronites drip water, dropwise and continue reaction 3-5h, obtained described super-hydrophobic ice-covering-proof coating; And each compounding substances is counted in mass ratio, silane coupling agent: silicon sol: the silane coupling agent that short fluorocarbon chain replaces: water is 1:0.20 ~ 0.50:0.01 ~ 0.05:1 ~ 3.
Preferably, the general structure of described silane coupling agent is:
Wherein, l is the integer of 1 ~ 4, and s is the integer of 1 ~ 18.
Preferably, the acidic silicasol that described silicon sol is take water as solvent, silicon-dioxide is solute, its pH value is 2 ~ 6, solid content is 30% ~ 50%, the particle diameter of silica dioxide granule is 10 ~ 100nm.
Preferably, the general structure of the silane coupling agent that described short fluorocarbon chain replaces is:
Wherein, n is the integer of 1 ~ 4, and m is the integer of 2 ~ 6; X is the combination of one or more in the alkylidene group of chain or ring dress, arylidene, sulfoamido, alkylsulfonyl, sulfonyloxy, carbonamido and carbon oxygen base.
Present invention also offers a kind of method preparing super-hydrophobic ice-covering-proof coating, comprise the following steps:
(1) under nitrogen protection, mixed by the silane coupling agent that silane coupling agent, silicon sol, short fluorocarbon chain replace, 40 DEG C ~ 80 DEG C following coronites drip water, dropwise and continue reaction 3-5h, obtain the anti-icing paint of hydrophobically modified; Wherein said silane coupling agent, silicon sol, the silane coupling agent of short fluorocarbon chain replacement and the mass ratio of water are 1:0.20 ~ 0.50:0.01 ~ 0.05:1 ~ 3;
(2) anti-icing paint obtained for step (1) is coated in substrate surface by the method for Dipping, then thermal treatment 3 ~ 5 hours at 80 ~ 120 DEG C, obtained super-hydrophobic ice-covering-proof coating.
Preferably, the general structure of described silane coupling agent is:
Wherein, l is the integer of 1 ~ 4, and s is the integer of 1 ~ 18.
Preferably, the acidic silicasol that described silicon sol is take water as solvent, silicon-dioxide is solute, sol pH is 2 ~ 6, solid content is 30% ~ 50%, the particle diameter of silica dioxide granule is 10 ~ 100nm.
Preferably, the general structure of the silane coupling agent that described short fluorocarbon chain replaces is:
Wherein, n is the integer of 1 ~ 4, and m is the integer of 2 ~ 6; X is one in the alkylidene group of chain or ring dress, arylidene, sulfoamido, alkylsulfonyl, sulfonyloxy, carbonamido and carbon oxygen base or its combination.
Further, the preparation process of described super-hydrophobic ice-covering-proof coating also comprises the process of described substrate surface; The process of described substrate surface is in the obtained paint of step (1) before substrate surface, is the alkaline soaked in absolute ethyl alcohol 3 ~ 7 days of 9 ~ 11 by substrate surface through pH.
Preferably, described base material is glass, silicon chip, metal.
The present invention has following advantage and effect relative to existing technology:
1) preparation of sol-gel method provided by the invention synthesis super-hydrophobic ice-covering-proof coating, coating adopts dipping method, technique very simple, also easy handling and promoting the use of on a large scale.
2) the present invention mainly realizes the super-hydrophobic ice-covering-proof performance of base material, good economy performance with the fluoro-containing group of alkyl group and minute quantity.
3) the present invention adopts fluorochemical monomer to be the silane coupling agent that short fluorocarbon chain replaces, avoid generally use in current anti-icing paint containing the organic fluorine material of long fluorocarbon chain to the harm of environment; And the present invention uses aqueous solvent; Therefore, the coating that prepared by the present invention is a kind of eco-friendly anti-icing paint.
4) further, also coated substrate is processed in the present invention, through the hydroxyl of the substrate surface of parlkaline soaked in absolute ethyl alcohol or carboxyl can with partial hydrolysis-condensation, the silica dioxide granule generation condensation reaction of surface containing hydroxyl, form interfacial bond, make ice-covering-proof coating of the present invention and substrate surface have good cohesiveness.
Embodiment
The low surface energy performance that the present invention mainly utilizes organic fluorine material to have and the hydrophobic performance containing alkyl material, the surface energy of coating is reduced by fluorine-containing organic group, improved the hydrophobicity of coating by alkyl group, based on this, prepare super-hydrophobic ice-covering-proof coating of the present invention.But form on homogeneous ideal surfaced in structure, even the minimum group of surface energy is tightly packed, its contact angle also less than 120 ° [Thin solid films, 2009,517 (17): 5001-5005].Therefore, be structure super hydrophobic surface, the present invention further utilizes inorganic particle silicon-dioxide and structure nano and micron composite structure of reuniting, and increases the surfaceness of hydrophobic matrix thus realizes super-hydrophobic performance.
Concrete, the raw materials of super-hydrophobic ice-covering-proof coating provided by the invention comprises containing alkyl material, organic fluorine material, silicon sol and water, and the first two component uses for reducing coatingsurface energy, and the latter uses for increasing the surfaceness of hydrophobic matrix.Wherein, what the present invention used is silane coupling agent containing alkyl material, and the general structure of preferred silane coupling agent is:
Wherein, l is the integer of 1 ~ 4, and s is the integer of 1 ~ 18.The organic fluorine material that the present invention uses is the silane coupling agent that short fluorocarbon chain replaces, and the general structure of the silane coupling agent of preferably this short fluorocarbon chain replacement is:
Wherein, n is the integer of 1 ~ 4, and m is the integer of 2 ~ 6; X is the one or more combination in the alkylidene group of chain or ring dress, arylidene, sulfoamido, alkylsulfonyl, sulfonyloxy, carbonamido and carbon oxygen base.Present invention uses the organic fluorine material that m is the short fluorocarbon chain of 2 ~ 6, avoid the organic fluorine material of the fluorocarbon chain structure using C>=8 in usual ice-covering-proof material, the organic fluorine material of the fluorocarbon chain structure that the anti-icing paint that the present invention is obtained and coating thereof overcome because using C>=8 is difficult to decomposition, environmentally hazardous shortcoming.The silicon sol that the present invention uses is: take water as solvent, the silicon-dioxide acidic silicasol that is solute, and the present invention preferably this silicon sol pH is 2 ~ 6, and solid content is 30% ~ 50%, and preferably the particle diameter of silica dioxide granule is 10 ~ 100nm further.The present invention utilizes inorganic particle silicon-dioxide and structure nano and micron composite structure of reuniting, increase the surfaceness of hydrophobic matrix and reach the super hydrophobic surface of ice-covering-proof coating, the super-hydrophobic coat overcome as the applying low surface energy shortcoming such as usually use the high cost of PTFE particle, micro mist surface-coated uneven.It is 1:0.20 ~ 0.50:0.01 ~ 0.05:1 ~ 3 that the mass ratio preparing each raw material of super-hydrophobic ice-covering-proof coating provided by the invention is preferably silane coupling agent, silicon sol, the silane coupling agent of short fluorocarbon chain replacement and the mass ratio of water.
Concrete, present invention utilizes sol-gel method and prepare super-hydrophobic ice-covering-proof coating of the present invention, the silane coupling agent that silicon sol, silane coupling agent, short fluorocarbon chain replace is mixed, slowly water is dripped 40 DEG C ~ 80 DEG C following coronites, dropwise and continue reaction 3-5h, obtain mutually reuniting between particle and the long colloidal sol having alkyl group and short fluorocarbon chain group in crosslinked surface, namely complete the preparation of super-hydrophobic ice-covering-proof coating of the present invention.Further this super-hydrophobic ice-covering-proof coating is coated to substrate surface by the method for Dipping, then after Overheating Treatment, forms super-hydrophobic ice-covering-proof coating at substrate surface.Wherein, preferred thermal treatment temp is 80 ~ 120 DEG C, and heat treatment time is 3 ~ 5 hours.Through this heat treatment process, the fluoro-containing group of silica sphere and carbochain can be made to move to coatingsurface, strengthen its hydrophobic performance.Further, the preparation process of super-hydrophobic ice-covering-proof coating of the present invention, also comprises substrate surface treatment; Concrete, before coating of the present invention is coated in substrate surface by dip coating, be the alkaline soaked in absolute ethyl alcohol 3 ~ 7 days of 9 ~ 11 through pH by substrate surface.Through the hydroxyl of the substrate surface of parlkaline soaked in absolute ethyl alcohol process or carboxyl can with partial hydrolysis-condensation, the silica dioxide granule generation condensation reaction of surface containing hydroxyl, forms interfacial bond, thus increases the cohesiveness of coating and substrate surface.
For a better understanding of the present invention, below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Under nitrogen protection, the silane coupling agent component C that silane coupling agent component A, silicon sol B component, short fluorocarbon chain replace is mixed, water D is slowly dripped 40 DEG C of following coronites, dropwise and continue reaction 3h, obtain the anti-icing paint of hydrophobically modified, the mass ratio of said components A, B, C and D is 1:0.20:0.01:1; I.e. obtained super-hydrophobic ice-covering-proof coating.
Being coated to through pH by the method for Dipping by the anti-icing paint of above-mentioned obtained hydrophobically modified is the slide surface of the alkaline soaked in absolute ethyl alcohol 3 days process of 9, thermal treatment 3 hours at 80 DEG C again, can obtain super-hydrophobic ice-covering-proof coating in this slide surface.
In the present embodiment, silane coupling agent component A is methyltrimethoxy silane, and silicon sol B component is pH=2, and solid content is 30%, particle diameter is the silicon dioxide gel of 10 ~ 100nm, and the silane coupling agent component C that short fluorocarbon chain replaces is perfluoro-ethyl propyl trimethoxy silicane.It is as shown in the table that the super-hydrophobic and anti-icing performance of the present embodiment gained functional paint detects data, and in table, " slide surface " refers to the test directly carried out in the slide surface of uncoated coating; Wherein surface static water contact angle and water roll angle utilize surface tension instrument to test, and anti-icing performance and water droplet measure at the freezing time of coatingsurface and utilize surface tension instrument and C203W low-temperature measurement pond jointly to measure, and low-temperature measurement pond is set as-18 DEG C.
| Project | Surface static water contact angle (°) | Water roll angle (°) | Anti-icing performance (s) |
| Embodiment 1 | 157 | 6 | 1704 |
| Slide surface | 33 | 64 | 107 |
Embodiment 2
Under nitrogen protection, the silane coupling agent component C that silane coupling agent component A, silicon sol B component, short fluorocarbon chain replace is mixed, water D is slowly dripped 40 DEG C of following coronites, dropwise and continue reaction 3h, obtain the anti-icing paint of hydrophobically modified, the mass ratio of said components A, B, C and D is 1:0.30:0.01:1; I.e. obtained super-hydrophobic ice-covering-proof coating.
Being coated to through pH by the method for Dipping by the anti-icing paint of above-mentioned obtained hydrophobically modified is the slide surface of the alkaline soaked in absolute ethyl alcohol 3 days process of 9, thermal treatment 3 hours at 80 DEG C again, namely cocoa obtains super-hydrophobic ice-covering-proof coating in this slide surface.
In this example, silane coupling agent component A is ethyl trimethoxy silane, and silicon sol B component is pH=2, and solid content is 30%, and particle diameter is the silicon dioxide gel of 10 ~ 100nm, and the silane coupling agent component C that short fluorocarbon chain replaces is perfluoro butyl sulfonyltriethoxylsilane.It is as shown in the table that the super-hydrophobic and anti-icing performance of the present embodiment gained functional paint detects data, and wherein projects testing method is identical with embodiment 1.
| Project | Surface static water contact angle (°) | Water roll angle (°) | Anti-icing performance (s) |
| Embodiment 2 | 166 | 6 | 1652 |
| Slide surface | 33 | 64 | 107 |
Embodiment 3
Under nitrogen protection, the silane coupling agent component C that silane coupling agent component A, silicon sol B component, short fluorocarbon chain replace is mixed, water D is slowly dripped 50 DEG C of following coronites, dropwise and continue reaction 4h, obtain the anti-icing paint of hydrophobically modified, the mass ratio of said components A, B, C and D is 1:0.50:0.01:1; I.e. obtained super-hydrophobic ice-covering-proof coating.
Being coated to through pH by the method for Dipping by the anti-icing paint of above-mentioned obtained hydrophobically modified is the silicon chip surface of the alkaline soaked in absolute ethyl alcohol 3 days process of 9, then thermal treatment 4 hours at 80 DEG C, can obtain super-hydrophobic ice-covering-proof coating at silicon chip surface.
In this example, silane coupling agent component A is butyl triethoxyl silane, and silicon sol B component is pH=4, and solid content is 30%, particle diameter is the silicon dioxide gel of 10 ~ 100nm, and the silane coupling agent component C that short fluorocarbon chain replaces is perfluoro hexyl sulfonamido Trimethoxy silane.It is as shown in the table that the super-hydrophobic and anti-icing performance of the present embodiment gained functional paint detects data, and wherein projects testing method is identical with embodiment 1.
| Project | Surface static water contact angle (°) | Water roll angle (°) | Anti-icing performance (s) |
| Embodiment 3 | 161 | 6 | 1711 |
| Silicon chip surface | 38 | 47 | 82 |
Embodiment 4
Under nitrogen protection, the silane coupling agent component C that silane coupling agent component A, silicon sol B component, short fluorocarbon chain replace is mixed, water D is slowly dripped 60 DEG C of following coronites, dropwise and continue reaction 5h, obtain the anti-icing paint of hydrophobically modified, the mass ratio of said components A, B, C and D is 1:0.50:0.02:2; I.e. obtained super-hydrophobic ice-covering-proof coating.
Being coated to through pH by the method for Dipping by the anti-icing paint of above-mentioned obtained hydrophobically modified is the silicon chip surface of the alkaline soaked in absolute ethyl alcohol 7 days process of 9, thermal treatment 5 hours at 100 DEG C again, can obtain super-hydrophobic ice-covering-proof coating at this silicon chip surface.
In this example, silane coupling agent component A is hexyl three propane TMOS, and silicon sol B component is pH=4, and solid content is 30%, particle diameter is the silicon dioxide gel of 10 ~ 100nm, and the silane coupling agent component C that short fluorocarbon chain replaces is perfluoro hexyl sulfonamido tripropoxy silane.It is as shown in the table that the super-hydrophobic and anti-icing performance of the present embodiment gained functional paint detects data, and wherein projects testing method is identical with embodiment 1.
| Project | Surface static water contact angle (°) | Water roll angle (°) | Anti-icing performance (s) |
| Embodiment 4 | 167 | 4 | 1623 |
| Silicon chip surface | 38 | 47 | 82 |
Embodiment 5
Under nitrogen protection, the silane coupling agent component C that silane coupling agent component A, silicon sol B component, short fluorocarbon chain replace is mixed, water D is slowly dripped 60 DEG C of following coronites, dropwise and continue reaction 3h, obtain the anti-icing paint of hydrophobically modified, the mass ratio of said components A, B, C and D is 1:0.50:0.03:3; I.e. obtained super-hydrophobic ice-covering-proof coating.
Being coated to through pH by the method for Dipping by the anti-icing paint of above-mentioned obtained hydrophobically modified is the iron plate surface of the alkaline soaked in absolute ethyl alcohol 7 days process of 11, thermal treatment 3 hours at 120 DEG C again, can obtain super-hydrophobic ice-covering-proof coating in this iron plate surface.
In this example, silane coupling agent component A is octyl group three butane TMOS, and silicon sol B component is pH=6, and solid content is 30%, particle diameter is the silicon dioxide gel of 10 ~ 100nm, and the silane coupling agent component C that short fluorocarbon chain replaces is perfluoro hexyl carbon acylamino three butoxy silane.It is as shown in the table that the super-hydrophobic and anti-icing performance of the present embodiment gained functional paint detects data, and wherein projects testing method is identical with embodiment 1.
| Project | Surface static water contact angle (°) | Water roll angle (°) | Anti-icing performance (s) |
| Embodiment 5 | 164 | 4 | 1475 |
| Iron plate surface | 35 | 51 | 47 |
Embodiment 6
Under nitrogen protection, the silane coupling agent component C that silane coupling agent component A, silicon sol B component, short fluorocarbon chain replace is mixed, water D is slowly dripped 80 DEG C of following coronites, dropwise and continue reaction 5h, obtain the anti-icing paint of hydrophobically modified, the mass ratio of said components A, B, C and D is 1:0.30:0.04:2; I.e. obtained super-hydrophobic ice-covering-proof coating.
Being coated to through pH by the method for Dipping by the anti-icing paint of above-mentioned obtained hydrophobically modified is the iron plate surface of the alkaline soaked in absolute ethyl alcohol 7 days process of 11, thermal treatment 5 hours at 80 DEG C again, can obtain super-hydrophobic ice-covering-proof coating in this iron plate surface.
In this example, silane coupling agent component A is dodecyl Trimethoxy silane, and silicon sol B component is pH=4, and solid content is 50%, particle diameter is the silicon dioxide gel of 10 ~ 100nm, and the silane coupling agent component C that short fluorocarbon chain replaces is perfluoro butyl carbon acylamino triethoxyl silane.It is as shown in the table that the super-hydrophobic and anti-icing performance of the present embodiment gained functional paint detects data, and wherein projects testing method is identical with embodiment 1.
| Project | Surface static water contact angle (°) | Water roll angle (°) | Anti-icing performance (s) |
| Embodiment 6 | 162 | 6 | 1615 |
| Iron plate surface | 35 | 51 | 47 |
Embodiment 7
Under nitrogen protection, the silane coupling agent component C that silane coupling agent component A, silicon sol B component, short fluorocarbon chain replace is mixed, water D is slowly dripped 60 DEG C of following coronites, dropwise and continue reaction 5h, obtain the anti-icing paint of hydrophobically modified, the mass ratio of said components A, B, C and D is 1:0.30:0.03:1; I.e. obtained super-hydrophobic ice-covering-proof coating.
Being coated to through pH by the method for Dipping by the anti-icing paint of above-mentioned obtained hydrophobically modified is the aluminium flake surface of the alkaline soaked in absolute ethyl alcohol 5 days process of 11, thermal treatment 3 hours at 120 DEG C again, can obtain super-hydrophobic ice-covering-proof coating in this aluminium flake surface.
In this example, silane coupling agent component A is n-hexadecyl triethoxyl silane, and silicon sol B component is pH=6, and solid content is 50%, particle diameter is the silicon dioxide gel of 10 ~ 100nm, and the silane coupling agent component C that short fluorocarbon chain replaces is perfluoro-ethyl methyltrimethoxy silane.It is as shown in the table that the super-hydrophobic and anti-icing performance of the present embodiment gained functional paint detects data, and wherein projects testing method is identical with embodiment 1.
| Project | Surface static water contact angle (°) | Water roll angle (°) | Anti-icing performance (s) |
| Embodiment 7 | 162 | 7 | 1617 |
| Aluminium flake surface | 33 | 63 | 79 |
Embodiment 8
Under nitrogen protection, the silane coupling agent component C that silane coupling agent component A, silicon sol B component, short fluorocarbon chain replace is mixed, water D is slowly dripped 70 DEG C of following coronites, dropwise and continue reaction 3h, obtain the anti-icing paint of hydrophobically modified, the mass ratio of said components A, B, C and D is 1:0.50:0.01:2; I.e. obtained super-hydrophobic ice-covering-proof coating.
Being coated to through pH by the method for Dipping by the anti-icing paint of above-mentioned obtained hydrophobically modified is the aluminium flake surface of the alkaline soaked in absolute ethyl alcohol 7 days process of 11, thermal treatment 5 hours at 120 DEG C again, can obtain super-hydrophobic ice-covering-proof coating in this aluminium flake surface.
In this example, silane coupling agent component A is Octadecane base three butane TMOS, and silicon sol B component is pH=2, and solid content is 50%, particle diameter is the silicon dioxide gel of 10 ~ 100nm, and the silane coupling agent component C that short fluorocarbon chain replaces is perfluoro butyl propyl trimethoxy silicane.It is as shown in the table that the super-hydrophobic and anti-icing performance of the present embodiment gained functional paint detects data, and wherein projects testing method is identical with embodiment 1.
| Project | Surface static water contact angle (°) | Water roll angle (°) | Anti-icing performance (s) |
| Embodiment 8 | 167 | 4 | 1509 |
| Aluminium flake surface | 33 | 63 | 79 |
Can be seen by above embodiment, ice-covering-proof coating of the present invention effectively can reduce contact area and the roll angle of water and substrate surface, the sticking power of drop and base material is reduced greatly, thus drop can must depart from substrate surface easily, especially external force is being had as under wind existent condition, making ice; In addition on the one hand, due between the super hydrophobic surface and supercooled water of low temperature occlusion a large amount of air, form a three phase boundary between drop and surface, change heat transfer process, thus effectively delayed freezing time, make drop have time enough to come off from surface, making ice.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under what other were any do not deviate from spirit of the present invention and principle, substitute, combine, simplify; be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a super-hydrophobic ice-covering-proof coating, it is characterized in that preparation process is: under nitrogen protection, the silane coupling agent that silane coupling agent, silicon sol, short fluorocarbon chain replace is mixed, 40 DEG C ~ 80 DEG C following coronites drip water, dropwise and continue reaction 3-5h, obtained described super-hydrophobic ice-covering-proof coating; And each compounding substances is counted in mass ratio, silane coupling agent: silicon sol: the silane coupling agent that short fluorocarbon chain replaces: water is 1:0.20 ~ 0.50:0.01 ~ 0.05:1 ~ 3.
2. the preparation method of a kind of super-hydrophobic ice-covering-proof coating according to claim 1, is characterized in that: the general structure of described silane coupling agent is:
Wherein, l is the integer of 1 ~ 4, and s is the integer of 1 ~ 18.
3. the preparation method of a kind of super-hydrophobic ice-covering-proof coating according to claim 1, it is characterized in that: the acidic silicasol that described silicon sol is take water as solvent, silicon-dioxide is solute, its pH value is 2 ~ 6, solid content is 30% ~ 50%, the particle diameter of silica dioxide granule is 10 ~ 100nm.
4. the preparation method of a kind of super-hydrophobic ice-covering-proof coating according to claim 1, is characterized in that: the general structure of the silane coupling agent that described short fluorocarbon chain replaces is:
Wherein, n is the integer of 1 ~ 4, and m is the integer of 2 ~ 6; X is the combination of one or more in the alkylidene group of chain or ring dress, arylidene, sulfoamido, alkylsulfonyl, sulfonyloxy, carbonamido and carbon oxygen base.
5. prepare a method for super-hydrophobic ice-covering-proof coating, it is characterized in that comprising the following steps:
(1) under nitrogen protection, mixed by the silane coupling agent that silane coupling agent, silicon sol, short fluorocarbon chain replace, 40 DEG C ~ 80 DEG C following coronites drip water, dropwise and continue reaction 3-5h, obtain the anti-icing paint of hydrophobically modified; Wherein said silane coupling agent, silicon sol, the silane coupling agent of short fluorocarbon chain replacement and the mass ratio of water are 1:0.20 ~ 0.50:0.01 ~ 0.05:1 ~ 3;
(2) anti-icing paint obtained for step (1) is coated in substrate surface by the method for Dipping, then thermal treatment 3 ~ 5 hours at 80 ~ 120 DEG C, obtained super-hydrophobic ice-covering-proof coating.
6. a kind of method preparing super-hydrophobic ice-covering-proof coating according to claim 5, is characterized in that: the general structure of described silane coupling agent is:
Wherein, l is the integer of 1 ~ 4, and s is the integer of 1 ~ 18.
7. a kind of method preparing super-hydrophobic ice-covering-proof coating according to claim 5, it is characterized in that: the acidic silicasol that described silicon sol is take water as solvent, silicon-dioxide is solute, sol pH is 2 ~ 6, solid content is 30% ~ 50%, the particle diameter of silica dioxide granule is 10 ~ 100nm.
8. a kind of method preparing super-hydrophobic ice-covering-proof coating according to claim 5, is characterized in that: the general structure of the silane coupling agent that described short fluorocarbon chain replaces is:
Wherein, n is the integer of 1 ~ 4, and m is the integer of 2 ~ 6; X is one in the alkylidene group of chain or ring dress, arylidene, sulfoamido, alkylsulfonyl, sulfonyloxy, carbonamido and carbon oxygen base or its combination.
9. a kind of method preparing super-hydrophobic ice-covering-proof coating according to any one of claim 5 to 8, is characterized in that: the preparation process of described super-hydrophobic ice-covering-proof coating also comprises the process of described substrate surface; The process of described substrate surface be by paint obtained for described step (1) before substrate surface, be the alkaline soaked in absolute ethyl alcohol 3 ~ 7 days of 9 ~ 11 through pH by substrate surface.
10. a kind of method preparing super-hydrophobic ice-covering-proof coating according to claim 9, described base material is glass, silicon chip, metal.
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| CN201510063187.4A CN104629620A (en) | 2015-02-06 | 2015-02-06 | Method for preparing superhydrophobic anti-icing paint and coating |
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| CN105670348A (en) * | 2015-11-27 | 2016-06-15 | 浙江大学 | All-lyophobic bionic anti-fouling self-cleaning coating and preparation method thereof |
| CN106220855A (en) * | 2016-08-30 | 2016-12-14 | 烟台德邦先进硅材料有限公司 | A kind of synthetic method of acrylate modified fluorine silicon coating |
| CN106221476A (en) * | 2016-08-27 | 2016-12-14 | 合肥普庆新材料科技有限公司 | A kind of preparation method of aqueous organic inorganic hybridization freezing coating |
| CN108102511A (en) * | 2017-12-28 | 2018-06-01 | 国网湖南省电力有限公司 | A kind of ice-phobic coating applied to transmission line of electricity and preparation method thereof |
| CN108504145A (en) * | 2018-04-03 | 2018-09-07 | 苏州大学 | A kind of super-hydrophobic film and preparation method thereof |
| CN108864624A (en) * | 2018-08-03 | 2018-11-23 | 苏州浩纳新材料科技有限公司 | A kind of rain-proof with microcellular structure declines radome and preparation method thereof |
| CN109650731A (en) * | 2019-01-16 | 2019-04-19 | 浙江大学自贡创新中心 | A kind of preparation method of self-cleaning glass coating |
| CN109880524A (en) * | 2019-01-16 | 2019-06-14 | 浙江大学自贡创新中心 | A kind of preparation method of vitreous coating liquid |
| CN111918825A (en) * | 2018-03-27 | 2020-11-10 | 东洋制罐集团控股株式会社 | Packaging member having surface with excellent liquid repellency |
| CN112774960A (en) * | 2020-12-18 | 2021-05-11 | 大唐浑源密马鬃梁新能源有限公司 | Coating process for anti-icing fan blade suitable for alpine region |
| CN114479656A (en) * | 2020-11-11 | 2022-05-13 | 杭州三花研究院有限公司 | Coating, preparation method of coating, heat exchanger containing coating and preparation method of heat exchanger |
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| CN111918825A (en) * | 2018-03-27 | 2020-11-10 | 东洋制罐集团控股株式会社 | Packaging member having surface with excellent liquid repellency |
| CN108504145A (en) * | 2018-04-03 | 2018-09-07 | 苏州大学 | A kind of super-hydrophobic film and preparation method thereof |
| CN108864624B (en) * | 2018-08-03 | 2020-11-27 | 苏州浩纳新材料科技有限公司 | Rain-proof radar cover with microporous structure and preparation method thereof |
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| CN109880524A (en) * | 2019-01-16 | 2019-06-14 | 浙江大学自贡创新中心 | A kind of preparation method of vitreous coating liquid |
| CN109650731A (en) * | 2019-01-16 | 2019-04-19 | 浙江大学自贡创新中心 | A kind of preparation method of self-cleaning glass coating |
| CN114479656A (en) * | 2020-11-11 | 2022-05-13 | 杭州三花研究院有限公司 | Coating, preparation method of coating, heat exchanger containing coating and preparation method of heat exchanger |
| CN114479656B (en) * | 2020-11-11 | 2024-05-03 | 杭州三花研究院有限公司 | Heat exchanger and preparation method thereof |
| CN112774960A (en) * | 2020-12-18 | 2021-05-11 | 大唐浑源密马鬃梁新能源有限公司 | Coating process for anti-icing fan blade suitable for alpine region |
| CN112774960B (en) * | 2020-12-18 | 2023-09-26 | 大唐浑源密马鬃梁新能源有限公司 | Coating process suitable for anti-icing fan blade in alpine region |
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