CN110434034A - Preparation method of super-hydrophobic coating - Google Patents
Preparation method of super-hydrophobic coating Download PDFInfo
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- CN110434034A CN110434034A CN201910788467.XA CN201910788467A CN110434034A CN 110434034 A CN110434034 A CN 110434034A CN 201910788467 A CN201910788467 A CN 201910788467A CN 110434034 A CN110434034 A CN 110434034A
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- Prior art keywords
- super
- hydrochloric acid
- preparation
- copper sheet
- hydrophobic coat
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- Granted
Links
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 title abstract description 10
- 238000000576 coating method Methods 0.000 title abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000010949 copper Substances 0.000 claims abstract description 71
- 229910052802 copper Inorganic materials 0.000 claims abstract description 71
- 238000005530 etching Methods 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 229960002668 sodium chloride Drugs 0.000 claims description 17
- 235000002639 sodium chloride Nutrition 0.000 claims description 17
- 239000011780 sodium chloride Substances 0.000 claims description 17
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 4
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 9
- 238000005470 impregnation Methods 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 2
- 230000003628 erosive effect Effects 0.000 abstract 1
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 238000003756 stirring Methods 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
- 229960000443 hydrochloric acid Drugs 0.000 description 6
- 235000011167 hydrochloric acid Nutrition 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 240000002853 Nelumbo nucifera Species 0.000 description 4
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 4
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 210000001595 mastoid Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention relates to a preparation method of a super-hydrophobic coating, wherein the etching method uses three different impregnation liquids to respectively impregnate for a period of time, so that the different impregnation liquids are used for impregnation to accelerate the etching rate, the specific proportion of the impregnation liquids is adopted to accelerate the etching rate, the lateral erosion amount and the protruding edge can be reduced by accelerating the etching rate, the micro-nano morphology formed on the surface of a copper sheet is more complex, and the hydrophobicity, the friction resistance and the folding resistance of the super-hydrophobic coating are improved; according to the invention, two kinds of fluorosilane and silane with similar boiling points can be better deposited on the surface of etched matrix copper, so that the coating has very low surface energy, the quality of the coating is stable, a good hydrophobic effect is achieved, the corrosion resistance and the cleanness of copper are better, and the service life is longer.
Description
Technical field
The invention belongs to super hydrophobic material technical fields, and in particular to a kind of preparation method of super-hydrophobic coat.
Background technique
Copper due to its have in major industry such as electric power sea military project with thermally conductive, conductive, anti-corrosion and processing performance it is important
Using.Such as condenser, the exchange piece of low-pressure heating and oil cooler and the sky of water-cooled generator of most of power industry
Core conducting wire is all Cu alloy material；It is also big in the water piping system in the military affairs battleship such as aircraft carrier in the war industry of ocean
It is mostly some copper products；Civilian aspect medical instrument, industrial vessel, Electronic Industry part etc. have the application of copper.But due to
Serious etching problem has been exposed in use and has brought limitation to the application of copper for copper product.
Super hydrophobic surface processing technique is a kind of novel anticorrosion technology, and super hydrophobic surface can play metal material
Automatically cleaning inhibits surface corrosion and surface oxidation and reduces the effect of coefficient of friction.It should be noted that super hydrophobic surface is
The common natural phenomena of nature is gathered for example, water and lotus leaf form the contact angle close to 170 ° when water droplet is fallen on lotus leaf
Collect beading without sprawling, extreme is hydrophobic.Free rolling may be implemented in water droplet on lotus leaf surface, when water droplet (such as rainwater, dew
Deng) roll when, the pollutants such as attachment dust on the surface can be taken away, so that surface be made to keep cleaning, such surface
For lotus leaf effect surface, also known as super hydrophobic surface.
There are many preparation method of hydrophobic surface, generally there is chemical method for etching, electrochemical process, photoetching process etc. both at home and abroad at present.
Etching technics is a kind of operation for damaging substrate surface after all, especially for the aluminum alloy base material of thin layer, etched
Mechanical performance will receive very big influence in journey, even result in substrate it is cracked or fracture, etch rate is low, existing etching
The micro-nano pattern on copper sheet surface is simple in method, thus the hydrophobic coating of preparation hydrophobic effect is poor, wearability and fold resistance
The problems such as poor.
For these reasons, the present invention is specifically proposed.
Summary of the invention
In order to solve problem above of the existing technology, the present invention provides a kind of preparation method of super-hydrophobic coat,
Lithographic method of the invention can accelerate the etch rate of copper sheet, reduce side etching quantity and nosing, the micro nano structure that surface is formed
It is more complicated, the hydrophobicity, wearability and fold resistance of super-hydrophobic coat can be increased.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of super-hydrophobic coat, the method include the following steps:
(1) substrate pre-processes: choosing copper sheet and derusts, successively with acetone, ethyl alcohol, deionized water ultrasonic cleaning, dries
It is spare；
(2) copper sheet etches: pretreated copper sheet being immersed in etching solution and reacts 12-24h, cleans three with deionized water
It is secondary, it dries spare；
(3) silicon fluoride, silane and the copper sheet etched are put into reaction kettle and carry out first time heating, be cooled to room temperature, put
Enter baking oven and carry out second of heating, forms super-hydrophobic coat on the surface of copper sheet.
Further, the copper sheet in step (1) successively passes through the sand of 400 mesh, 600 mesh, 1000 mesh, 1500 mesh, 2000 mesh
Paper carries out polishing derusting.
Further, etching described in step (2) is first to be immersed in copper sheet in the mixed solution of sodium chloride and hydrochloric acid
4-8h is cleaned up with deionized water, is dried, then is immersed in 4-10h in the mixed solution of hydrogen peroxide and hydrochloric acid, uses deionized water
Cleaning, dries, is immersed in 4-6h in the mixed solution of iron chloride and hydrochloric acid again.
Lithographic method in the present invention carries out time of infusion using three kinds of different maceration extracts respectively,
Matrix not only may be used by being immersed in the mixing etching liquid of different special ratios and increasing the stirring of different directions
To accelerate etch rate, reduce side etching quantity, edge nosing and avoid local etching, can also obtain sufficiently complex compound micro-
Nanostructure forms appropriate roughness in matrix surface, makes its surface that the groove array of bar shaped, the depth of groove both be distributed with
And size is irregular, and is uniformly distributed there are many small graininess mastoid process and micropore, raised bulk has different rulers again above
Very little small gully, this advantageously reduces the area of water and substrate contact, lays a solid foundation for building super-hydrophobic coat.
In order to avoid local etching and etching edge occur for copper sheet, keep matrix etching uniform, to etching in etching process
When liquid progress vertical stirring or horizontal stirring and ultrasound etches.Etching liquid and copper sheet three mouthfuls of round bottoms are packed into when vertical stirring to burn
Bottle, is fixed in iron stand, and stirring rod is vertically positioned above copper sheet, adjusts mixing speed in 200-270r/min, raising is stirred
Etch rate can be increased by mixing rate.When level stirring, etching liquid and copper sheet are fitted into beaker, one is fixed by ultrasonic machine
Can be with the iron stand of left-right rotation, stirring rod is horizontal positioned, stirring rate 150-200r/min, and in stirring, ultrasound can simultaneously
So that etching is more uniform.
Further, the mixed solution of sodium chloride and hydrochloric acid is the sodium-chloride water solution and quality point that concentration is 1-2mol/L
Number is that 10-20% hydrochloric acid solution mixes in equal volume.
Further, the mixed solution of hydrogen peroxide and hydrochloric acid is the hydrogen peroxide and mass fraction that mass fraction is 14-16%
It is mixed in equal volume for the hydrochloric acid solution of 10-20%.
Further, it is 5-10% ferric chloride in aqueous solution and quality point that the mixed solution of iron chloride and hydrochloric acid, which is mass fraction,
Number is that the hydrochloric acid solution of 30-40% mixes in equal volume.
Further, the volume ratio of silicon fluoride and silane is 1:1-2 in step (3).
Further, the silicon fluoride is ten trifluoro zinc-base triethoxysilanes, and the silane is octadecyl three
Methoxy silane.
Further, the temperature of heating is 130-140 DEG C for the first time in step (3), heating time 3-4h.
Further, the temperature of second of heating is 165-170 DEG C in step (3), heating time 1.8-2.2h.
Heating purpose is that the silicon fluoride of liquid, silane is allowed to become gaseous deposit in copper sheet surface, second of heating for the first time
Purpose be to vapor away liquid silicon fluoride, the silane of copper sheet excess surface.
Compared with prior art, the invention has the benefit that
(1) lithographic method in the present invention carries out time of infusion using three kinds of different maceration extracts respectively, and matrix is logical
It crosses and is immersed in the mixing etching liquid of different special ratios and increases the stirrings of different directions and can not only accelerate etch rate,
Reduce side etching quantity, edge nosing and avoid local etching, sufficiently complex composite micro-nano rice structure can also be obtained, in matrix
Surface forms appropriate roughness, makes its surface that the groove array of bar shaped both be distributed with, the depth and size of groove are irregular, again
It being uniformly distributed there are many small graininess mastoid process and micropore, raised bulk has various sizes of small gully again above, this
The area of water and substrate contact is advantageously reduced, is laid a solid foundation for building super-hydrophobic coat；Increase copper sheet surface to be formed
Micro-nano pattern complexity, increase hydrophobicity, rub resistance and the fold resistance of super-hydrophobic coat；
(2) silicon fluoride, silane similar in two kinds of boiling points of present invention selection can preferably be deposited on the matrix copper etched
Surface, is formed on its surface stable, the preferable super-hydrophobic coat of hydrophobic effect, and the alkoxy of silicon fluoride and silane is in water environment
The silicone hydroxyl that the middle silicone hydroxyl that stepwise hydrolysis formation high activity occurs can be adsorbed with copper surface form perfect hydrogen bond knot
It closes, and can also mutually carry out dehydration between silicone hydroxyl and form oligomer Si-O-Si, unreacted silicone hydroxyl and copper surface
Extra hydroxyl with covalent bonding, silicon fluoride, silane thin layer can stably depositing in metal surface, there is coating very low
Surface can, so that coating quality is more stable, reach good hydrophobic effect so that the corrosion resistance of copper and spatter property are more preferable,
The service life is longer.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the scanning electron microscope (SEM) photograph after 2 copper sheet of embodiment of the present invention etching；
Fig. 2 is the scanning electron microscope (SEM) photograph of super-hydrophobic coat prepared by the embodiment of the present invention 2；
Fig. 3 is the scanning electron microscope (SEM) photograph after 1 copper sheet of comparative example etching of the present invention；
Fig. 4 is the scanning electron microscope (SEM) photograph of super-hydrophobic coat prepared by comparative example 1 of the present invention；
Fig. 5 is the scanning electron microscope (SEM) photograph after 2 copper sheet of comparative example etching of the present invention；
Fig. 6 is the scanning electron microscope (SEM) photograph of super-hydrophobic coat prepared by comparative example 2 of the present invention；
Fig. 7 is the scanning electron microscope (SEM) photograph after 3 copper sheet of comparative example etching of the present invention；
Fig. 8 is the scanning electron microscope (SEM) photograph of super-hydrophobic coat prepared by comparative example 3 of the present invention；
Fig. 9 is the contact angle figure of super-hydrophobic coat prepared by the embodiment of the present invention 2.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Embodiment 1
A kind of preparation method of super-hydrophobic coat of the present embodiment, the method include the following steps:
(1) substrate pre-processes: selection diameter is that 1cm successively passes through on copper sheet surface with a thickness of the round copper sheet of 0.2mm
400 mesh, 600 mesh, 1000 mesh, 1500 mesh, 2000 mesh sand paper carry out polishing derusting, it is successively super with acetone, ethyl alcohol, deionized water
Sound clean the surface grease stain and other impurities are dried spare；
(2) copper sheet etches: copper sheet is first immersed in 4h in the mixed solution of sodium chloride and hydrochloric acid, sodium chloride and hydrochloric acid it is mixed
Conjunction solution is the sodium-chloride water solution that concentration is 1mol/L and mass fraction is that 10% hydrochloric acid solution mixes in equal volume, is spent
Ionized water cleans up, and dries, then is immersed in 4h in the mixed solution of hydrogen peroxide and hydrochloric acid, the mixed solution of hydrogen peroxide and hydrochloric acid
For mass fraction be 14% hydrogen peroxide and mass fraction be 10% hydrochloric acid solution mix in equal volume, it is clear with deionized water
It washes, dries, be immersed in 4h in the mixed solution of iron chloride and hydrochloric acid again, the mixed solution of iron chloride and hydrochloric acid is mass fraction
The hydrochloric acid solution for being 5% for 30% ferric chloride in aqueous solution and mass fraction mixes in equal volume, is cleaned three times with deionized water,
It dries spare, wherein etching liquid and copper sheet are packed into three neck round bottom flask, are fixed on iron stand by vertical stirring in etching process
In, stirring rod is vertically positioned above copper sheet, adjusts mixing speed in 235r/min；
(3) by ten trifluoro zinc-base triethoxysilanes and octadecyl trimethoxysilane according to volume ratio 1:1, total volume
For 0.2ml, and the copper sheet that has etched is put into reaction kettle and carries out first time heating, and the temperature of heating is 130 DEG C, and heating time is
4h is cooled to room temperature, and is put into baking oven and is carried out second of heating, the temperature of heating is 165 DEG C, heating time 2.2h, in copper sheet
Surface formed super-hydrophobic coat.
Embodiment 2
A kind of preparation method of super-hydrophobic coat of the present embodiment, the method include the following steps:
(1) substrate pre-processes: selection diameter is that 1cm successively passes through on copper sheet surface with a thickness of the round copper sheet of 0.2mm
400 mesh, 600 mesh, 1000 mesh, 1500 mesh, 2000 mesh sand paper carry out polishing derusting, it is successively super with acetone, ethyl alcohol, deionized water
Sound clean the surface grease stain and other impurities are dried spare；
(2) copper sheet etches: copper sheet is first immersed in 6h in the mixed solution of sodium chloride and hydrochloric acid, sodium chloride and hydrochloric acid it is mixed
Conjunction solution is the sodium-chloride water solution that concentration is 1.5mol/L and mass fraction is that 15% hydrochloric acid solution mixes in equal volume, is used
Deionized water cleans up, and dries, then is immersed in 7h in the mixed solution of hydrogen peroxide and hydrochloric acid, and the mixing of hydrogen peroxide and hydrochloric acid is molten
The hydrochloric acid solution that liquid is the hydrogen peroxide that mass fraction is 15% and mass fraction is 15% mixes in equal volume, uses deionized water
Cleaning, dries, and is immersed in 5h in the mixed solution of iron chloride and hydrochloric acid again, and the mixed solution of iron chloride and hydrochloric acid is quality point
Number is that the hydrochloric acid solution that 35% ferric chloride in aqueous solution and mass fraction are 7.5% mixes in equal volume, is cleaned with deionized water
Three times, it dries spare, wherein horizontal stirring is selected in etching process, etching liquid and copper sheet are fitted into beaker, solid by ultrasonic machine
Fixed one can be with the iron stand of left-right rotation, and stirring rod is horizontal positioned, stirring rate 180r/min；
(3) overall by ten trifluoro zinc-base triethoxysilanes and octadecyl trimethoxysilane according to volume ratio 1:1.4
Product is 0.3ml, and the copper sheet etched is put into reaction kettle and carries out first time heating, and the temperature of heating is 135 DEG C, heating time
It for 3.5h, is cooled to room temperature, is put into baking oven and carries out second of heating, the temperature of heating is 167 DEG C, heating time 2h, in copper
The surface of piece forms super-hydrophobic coat.
Embodiment 3
A kind of preparation method of super-hydrophobic coat of the present embodiment, the method include the following steps:
(1) substrate pre-processes: selection diameter is that 1cm successively passes through on copper sheet surface with a thickness of the round copper sheet of 0.2mm
400 mesh, 600 mesh, 1000 mesh, 1500 mesh, 2000 mesh sand paper carry out polishing derusting, it is successively super with acetone, ethyl alcohol, deionized water
Sound clean the surface grease stain and other impurities are dried spare；
(2) copper sheet etches: copper sheet is first immersed in 8h in the mixed solution of sodium chloride and hydrochloric acid, sodium chloride and hydrochloric acid it is mixed
Conjunction solution is the sodium-chloride water solution that concentration is 2mol/L and mass fraction is that 20% hydrochloric acid solution mixes in equal volume, is dried in the air
It is dry, then it is immersed in 10h in the mixed solution of hydrogen peroxide and hydrochloric acid, it is 16% that the mixed solution of hydrogen peroxide and hydrochloric acid, which is mass fraction,
Hydrogen peroxide and mass fraction be 20% hydrochloric acid solution mix in equal volume, cleaned, dried with deionized water, iron chloride and
The mixed solution of hydrochloric acid is that the hydrochloric acid solution that mass fraction is 40% ferric chloride in aqueous solution and mass fraction is 10% mixes in equal volume
Close, cleaned three times with deionized water, dry it is spare wherein, etching liquid and copper sheet are packed by vertical stirring in etching process
Three neck round bottom flask is fixed in iron stand, and stirring rod is vertically positioned above copper sheet, adjusts mixing speed in 250r/min；
(3) by ten trifluoro zinc-base triethoxysilanes and octadecyl trimethoxysilane according to volume ratio 1:2, total volume
For 0.4ml, and the copper sheet that has etched is put into reaction kettle and carries out first time heating, and the temperature of heating is 140 DEG C, and heating time is
3h is cooled to room temperature, and is put into baking oven and is carried out second of heating, the temperature of heating is 170 DEG C, heating time 1.8h, in copper sheet
Surface formed super-hydrophobic coat.
The scanning electron microscope (SEM) photograph after copper sheet etching in embodiment 2 is as shown in Figure 1, super-hydrophobic coat prepared by embodiment 2
Scanning electron microscope (SEM) photograph as shown in Fig. 2, the present inventor has also done the almost the same of scanning electron microscope (SEM) photograph and embodiment 2 to embodiment 1 and 3,
Since length is limited, do not enumerating.
Comparative example 1
The preparation method of the super-hydrophobic coat of this comparative example is same as Example 2, the difference is that, in step (2)
Etching is only with the mixed solution impregnation in sodium chloride and hydrochloric acid, wherein scanning electron microscope (SEM) photograph such as Fig. 3 institute after copper sheet etching
Show, the scanning electron microscope (SEM) photograph of the super-hydrophobic coat of this comparative example preparation is as shown in Figure 4.
Comparative example 2
The preparation method of the super-hydrophobic coat of this comparative example is same as Example 2, the difference is that, in step (2)
Etching is only with the mixed solution impregnation in hydrogen peroxide and hydrochloric acid, wherein scanning electron microscope (SEM) photograph such as Fig. 5 institute after copper sheet etching
Show, the scanning electron microscope (SEM) photograph of the super-hydrophobic coat of this comparative example preparation is as shown in Figure 6.
Comparative example 3
The preparation method of the super-hydrophobic coat of this comparative example is same as Example 2, the difference is that, in step (2)
Etching is only with the mixed solution impregnation in iron chloride and hydrochloric acid, wherein scanning electron microscope (SEM) photograph such as Fig. 7 institute after copper sheet etching
Show, the scanning electron microscope (SEM) photograph of the super-hydrophobic coat of this comparative example preparation is as shown in Figure 8.
The test method of hydrophobic performance in the present invention: it with contact angle tester measurement water droplet in film surface contact angle, connects
Feeler value obtains after being averaged by 5 random site measurements, and static contact angle uses drop method (sessile drop) measurement of lying,
When super hydrophobic surface (i.e. static contact angle is greater than 150 ° of surface) measurement, when measurement, uniformly uses 5 μ L water droplets.
Test example 1
According to above-mentioned hydrophobic performance test method, the respectively super-hydrophobic painting of testing example 1-3 and comparative example 1-3 preparation
The contact angle size of the copper sheet of layer, the results are shown in Table 1.
Table 1
| Group | Contact angle (°) |
| Embodiment 1 | 165.12 |
| Embodiment 2 | 166.47 |
| Embodiment 3 | 164.56 |
| Comparative example 1 | 135.94 |
| Comparative example 2 | 144.87 |
| Comparative example 3 | 146.49 |
From table 1 it follows that big using the contact angle of super-hydrophobic coat made from method of the invention, i.e. hydrophobic performance
Good, the contact angle of comparative example 1-3 is substantially reduced, this is because the etching of copper sheet is performed etching and can be added using method of the invention
Fast etch rate can reduce side etching quantity and nosing, and the micro-nano pattern that copper sheet surface is formed is increasingly complex, increase super-hydrophobic
The contact angle of the hydrophobicity of coating, super-hydrophobic coat prepared by embodiment 2 is as shown in Figure 9.
Test example 2
The embodiment 1-3 and comparative example 1-3 copper sheet with super-hydrophobic coat prepared is placed in the chlorine that mass fraction is 5%
Change and corroded in sodium water solution, measures the size of the contact angle of different etching times, the results are shown in Table 2.
Table 2
From table 2 it can be seen that the super-hydrophobic coat of preparation of the invention is compared with comparative example 1-3 with preferable corrosion-resistant
Performance impregnates 18 days in sodium chloride and still shows preferable hydrophobicity.
Test example 3
It carries out the embodiment 1-3 and comparative example 1-3 copper sheet with super-hydrophobic coat prepared to bend different numbers respectively,
The contact angle for measuring each coating, the results are shown in Table 3.
Table 3
From table 3 it can be seen that super-hydrophobic coat prepared by the present invention contact angle still with higher after bending 30 times,
Contact angle reduction is unobvious, illustrates the bend resistance better performances of super-hydrophobic coat prepared by the present invention.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of preparation method of super-hydrophobic coat, which is characterized in that the method includes the following steps:
(1) substrate pre-processes: choosing copper sheet and derusts, successively with acetone, ethyl alcohol, deionized water ultrasonic cleaning, dries spare；
(2) copper sheet etches: pretreated copper sheet is immersed in etching solution and reacts 12-24h, is cleaned three times with deionized water,
It dries spare；
(3) silicon fluoride, silane and the copper sheet etched are put into reaction kettle and carry out first time heating, be cooled to room temperature, be put into baking
Case carries out second and heats, and forms super-hydrophobic coat on the surface of copper sheet.
2. the preparation method of super-hydrophobic coat according to claim 1, which is characterized in that the copper sheet in step (1) is successively
Polishing derusting is carried out by the sand paper of 400 mesh, 600 mesh, 1000 mesh, 1500 mesh, 2000 mesh.
3. the preparation method of super-hydrophobic coat according to claim 1, which is characterized in that etching described in step (2)
For copper sheet to be first immersed in 4-8h in the mixed solution of sodium chloride and hydrochloric acid, is cleaned up, dried with deionized water, then be immersed in
4-10h in the mixed solution of hydrogen peroxide and hydrochloric acid, is cleaned with deionized water, is dried, and is immersed in the mixed of iron chloride and hydrochloric acid again
Close 4-6h in solution.
4. the preparation method of super-hydrophobic coat according to claim 3, which is characterized in that the mixing of sodium chloride and hydrochloric acid is molten
Liquid is the sodium-chloride water solution that concentration is 1-2mol/L and mass fraction is that 10-20% hydrochloric acid solution mixes in equal volume.
5. the preparation method of super-hydrophobic coat according to claim 3, which is characterized in that the mixing of hydrogen peroxide and hydrochloric acid is molten
The hydrochloric acid solution that liquid is the hydrogen peroxide that mass fraction is 14-16% and mass fraction is 10-20% mixes in equal volume.
6. the preparation method of super-hydrophobic coat according to claim 3, which is characterized in that the mixing of iron chloride and hydrochloric acid is molten
Liquid is that the hydrochloric acid solution that mass fraction is 30-40% ferric chloride in aqueous solution and mass fraction is 5-10% mixes in equal volume.
7. the preparation method of super-hydrophobic coat according to claim 1, which is characterized in that silicon fluoride and silicon in step (3)
The volume ratio of alkane is 1:1-2.
8. the preparation method of super-hydrophobic coat according to claim 1 or claim 7, which is characterized in that the silicon fluoride is ten
Trifluoro zinc-base triethoxysilane, the silane are octadecyl trimethoxysilane.
9. the preparation method of super-hydrophobic coat according to claim 1, which is characterized in that heated for the first time in step (3)
Temperature be 130-140 DEG C, heating time 3-4h.
10. the preparation method of super-hydrophobic coat according to claim 1, which is characterized in that heated for second in step (3)
Temperature be 165-170 DEG C, heating time 1.8-2.2h.
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