CN108441897A - A kind of processing drop pie bounces the electrocasting methods of super-hydrophobic columnar arrays - Google Patents
A kind of processing drop pie bounces the electrocasting methods of super-hydrophobic columnar arrays Download PDFInfo
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- CN108441897A CN108441897A CN201810385926.5A CN201810385926A CN108441897A CN 108441897 A CN108441897 A CN 108441897A CN 201810385926 A CN201810385926 A CN 201810385926A CN 108441897 A CN108441897 A CN 108441897A
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- electroforming
- hydrophobic
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- waxed
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/10—Moulds; Masks; Masterforms
Abstract
The invention belongs to micro electroforming processing technique field, it is related to a kind of processing drop pie and bounces the electrocasting methods of super-hydrophobic columnar arrays.The concentrated sulfuric acid solution that metallic substrates are put into 6mol/L carries out acid etching activation, then through deionized water ultrasonic cleaning, is pre-processed；Waxed dose of spin coating in copper coin substrate is put into drying box first 65 DEG C of 30~40min of preliminary drying, then 85 DEG C of front baking 60min, processes metal array blind hole structure using drill bit after being cooled to room temperature, obtain electroforming core model；Using electroforming core model as template, using phosphor-copper as anode, carries out eletroforming and go out columnar arrays；Waxed core model after the completion of electroforming is heated in an oven, after wax-pattern all melts loss, then is cleaned in cleaning agent；It is finally modified with the ethanol solution of low-surface-energy material, is dried after taking-up and can be obtained super-hydrophobic cylindrical-array.The cylindrical-array size that operating procedure of the present invention is simple, controllability is good, pollution is small, at low cost, prepared is big.
Description
Technical field
The invention belongs to micro electroforming processing technique fields, are related to a kind of super-hydrophobic columnar arrays of processing drop pie spring
Electrocasting method.
Background technology
Sleet is a kind of common natural calamity, is easily caused brokenly to the production and living of the mankind in solid surface-attached icing
It is bad, such as electric wire, aircraft, wind turbine, refrigeration system etc., cause operational efficiency to reduce, in some severe cases, also
Can cause death accident.Mechanical deicing's Defrost method takes time and effort, and can also cause to damage to frozen surface.In this regard, researcher
More efficient way is constantly looked for inhibit or postpone the formation of frost.
Super hydrophobic surface has larger contact angle and smaller roll angle, and drop shock will produce bounce thereon, and general
Logical surface orients transport field compared to that can effectively reduce liquid-solid time of contact, in automatically cleaning, freezing frosting, corrosion-resistant, drop
It is interesting.In recent years the study found that the super hydrophobic surface with special construction can be further reduced the liquid-solid contact time, especially
It will appear pie bounce when drop is hit in super-hydrophobic columnar arrays, the liquid-solid contact time can be greatly decreased, antifreeze
Rain freezing etc. is significant.Currently, the method for preparing the super-hydrophobic columnar arrays that drop pie spring can be achieved has very
It is more.Liu et al. processes about 20 μm~100 μm of diameter using the method that Wire EDM and chemical solution etch on copper coin,
Highly 800 μm~1200 μm of super-hydrophobic taper array and square column array will appear pie spring after droplets impact, liquid-solid to connect
Touch time reduction 80%.(Liu,Y.,Moevius,L.,Xu,X.,Qian,T.,Yeomans,J.M.,&Wang,Z..Nature
Physics 2014,10,515-519), however, such structure at present can only since diameter is too small and ratio of height to diameter is excessive
It is processed with electric spark wire cutting method.But electrical discharge machining efficiency is too low, and processing 2cm × 2cm samples need 7~8 hours, it is difficult to
Realize the processing of industrialization large area.Song etc. use polymer for matrix by template process a diameter of 0.8mm~
1.25mm is highly 0.6mm~1.0mm columnar arrays, then so that its surface super hydrophobic is obtained super-hydrophobic column battle array by spray coating method
Row.(Song, J., Gao, M., Zhao, C., Lu, Y., Huang, L. , ＆Liu, X., et al.Acs Nano, 2017,11,
9259-9267), although large area processing may be implemented in this method, but not applicable for metal material, and technics comparing is multiple
It is miscellaneous, it needs to dissolve template using strong acid, can cause environmental pollution.Therefore, it is necessary to develop a kind of new safety, ring
It protects, process is simple and is suitble to the technique of large area processing on the metal material to prepare the super of achievable drop pie spring
The method of hydrophobic columnar arrays.
Invention content
The present invention proposes a kind of processing drop pie and bounces the electrocasting methods of super-hydrophobic columnar arrays, can not only realize gold
Belong to drop pie spring in substrate, and is suitble to the technique of large area industrialization processing again.The present invention mainly proposes column diameter
0.5mm~1.5mm, intercolumniation 0.25mm highly can also realize drop pie for the super-hydrophobic cylindrical-array of 0.8mm~1.0mm
Spring, and propose using gypsum or wax to be that core model progress eletroforming pie bounces the methods of super-hydrophobic columnar arrays.
Technical scheme of the present invention：
A kind of processing drop pie bounces the electrocasting methods of super-hydrophobic columnar arrays, and steps are as follows：
(1) metallic substrates pre-process：Metal copper plate is first cleaned into oil removing, then puts it into the concentrated sulfuric acid solution of 6mol/L
Acid etching activation is carried out, then through deionized water ultrasonic cleaning, drying；Etch period is no less than 3min；
(2) electroforming core model is prepared：Waxed dose of spin coating first in copper coin substrate, then put it into drying box first with
65 DEG C of 30~40min of preliminary drying recycle 85 DEG C of front baking 60min, make waxed dose to be adhering closely in copper coin substrate, be cooled to room temperature
Metal being processed in wax dosage surface using drill bit afterwards and displaying blind hole structure, electroforming core model is obtained after polishing, cleaning and drying；
Waxed dose of thickness of the spin coating is 0.5~2mm；The core model material is one kind in paraffin, beeswax, gypsum, photoresist
Or a variety of mixing；
(3) eletroforming：By with waxed core model metal copper plate and phosphorus copper plate Parallel Symmetric place, and pass through conducting wire phase
Even power supply, using metal copper plate as cathode, phosphor-copper makes to be full of electroforming between anode and cathode by electrolyte circulation system as anode
Liquid carries out eletroforming；Used electroforming solution is the H of 0.5mol/L~1mol/L2SO4Aqueous solution, CUSO4·H2O aqueous solutions
Or cupric pyrophosphate electroforming solution, copper cyanider electroforming solution, cupric fluoborate electroforming solution；Process time is no less than 60min；The electroforming adds
It should be controlled in 2~10A/dm with the product of current density between working hour2；
(4) modulus：Waxed core model after the completion of electroforming is heated in an oven, after wax-pattern all melts loss, then clear
It is cleaned in lotion；
(5) super-hydrophobic processing：The electroforming cylindrical-array that step (4) obtains is put into the ethanol solution of low-surface-energy material
It is modified, is dried after taking-up and can be obtained super-hydrophobic cylinder display；The mass fraction of low-surface-energy material ethanol solution is more than
0.1%, the modification time is not less than 30min；The low-surface-energy material is silicon fluoride, stearic acid, palmitic acid, lauric acid, meat
One or more mixing in myristic acid.
Beneficial effects of the present invention：
(1) present invention is without complicated processing unit (plant) and operating procedure, and easily prepared by large area.
(2) present invention can accurately copy the surface topography of core model, and the columnar arrays height that electroforming comes out can be from zero
Several millimeters to several millimeters of point.
(3) present invention is easy to get the Multi-layer structure member by different metal or metal and nonmetallic combination.Such as replace electroforming
After liquid, different columnar metal arrays can be obtained.
(4) the waxed or gypsum agent core model that the present invention uses is of low cost, can be melted stripping, operation letter in an oven
It is single and environmentally safe.
(5) the electroforming solution environmental pollution of the invention used is small, ingredient is simple, easy to maintain and cost is relatively low.
Description of the drawings
Fig. 1 is that the waxed core model of embodiment 1 processes the schematic diagram of super-hydrophobic cylindrical-array.
In figure：1 copper coin；2 waxed core models；3 drill bits；4 eletroformings；5 electroforming metal layers；6 phosphor-coppers (anode)；7 heating；8
Silicon fluoride processing.
Fig. 2 is the experimental provision schematic diagram of embodiment 1.
Specific implementation mode
Below in conjunction with attached drawing and technical solution, the specific implementation mode that further illustrates the present invention.
Embodiment 1：
(1) metallic substrates pre-process
First by metal copper plate that size is 100mm × 80mm, (actual processing size is 90mm × 90mm, and redundance plays dress
Folder and electric action) washes of absolute alcohol oil removing is used, the concentrated sulfuric acid solution for then putting it into 6mol/L carries out acid etching activation
3min ensures that electroformed layer and matrix have good binding force, is cleaned later with a large amount of deionized waters, reuse ultrasonic cleaning
5min is used in combination hair-dryer to dry up.
(2) electroforming core model is prepared
Then waxed dose of spin coating first in copper coin substrate, thickness 1mm are put it into pre- first with 65 DEG C in drying box
30min is dried, 85 DEG C of front baking 60min are recycled.After being cooled to room temperature；Metal diameter 1.00mm, column are processed by Drill Techniques
The array blind hole structure of spacing 0.25mm, depth 1mm are polished using 1500# sand paper and remove surface spikes, and super through deionized water
It is dried up after sound cleaning.
(3) eletroforming
Cathode will be connected with the metal copper plate of waxed core model, by the phosphorus copper plate (redundance that size is 90 × 90mm
Clamping and electric action) jointed anode, the spacing of negative and positive interpolar is 5mm.Make to fill between anode and cathode by electrolyte circulation system
Full 1mol/L H2SO4、CUSO4·H2O mixed aqueous solutions, and the additives such as appropriate brightener are added.In 10A/dm2Electric current it is close
Degree is lower to stir electroforming 60min using high speed rotor, obtains the copper electroforming cylindrical-array with diameter 1.00mm.After processing, go
Ionized water ultrasonic cleaning 5min, is used in combination hair-dryer to dry up.
(4) modulus
The extra electroformed layer overflowed from hole in step (3) is blocked, puts and heats 1 hour in an oven, wax-pattern all melts
After loss, then cleaned up in cleaning agent.
(5) super-hydrophobic processing
The tridecafluoro-n-octyltriethoxysilane that the electroforming cylindrical-array merging mass fraction that step (4) is obtained is 1%
Ethanol solution in impregnate 45min, put it into after taking-up in baking oven and dry 20min at 80 DEG C, room is naturally cooled to after taking-up
Temperature has obtained the super-hydrophobic cylindrical-array of metal copper plate substrate.Contact angle of the water droplet on the super-hydrophobic cylindrical-array surface of Copper substrate
It it is 150 °, roll angle is 2 °.
Claims (3)
- The electrocasting method of super-hydrophobic columnar arrays 1. a kind of processing drop pie bounces, which is characterized in that steps are as follows：(1) metallic substrates pre-process：Metal copper plate is first cleaned into oil removing, the concentrated sulfuric acid solution for then putting it into 6mol/L carries out Acid etching activates, then through deionized water ultrasonic cleaning, drying；Etch period is no less than 3min；(2) electroforming core model is prepared：Then waxed dose of spin coating first in copper coin substrate is put it into drying box first with 65 DEG C 30~40min of preliminary drying recycles 85 DEG C of front baking 60min, makes waxed dose to be adhering closely in copper coin substrate, profit after being cooled to room temperature Metal being processed in wax dosage surface with drill bit and displaying blind hole structure, electroforming core model is obtained after polishing, cleaning and drying；It is described Waxed dose of thickness of spin coating be 0.5~2mm；(3) eletroforming：By with waxed core model metal copper plate and phosphorus copper plate Parallel Symmetric place, and pass through conducting wire be connected electricity Source, using metal copper plate as cathode, phosphor-copper makes to be full of electroforming solution between anode and cathode by electrolyte circulation system as anode, into Row eletroforming；Used electroforming solution is the H of 0.5mol/L~1mol/L2SO4Aqueous solution, CUSO4·H2O aqueous solutions or coke Cupric phosphate electroforming solution, copper cyanider electroforming solution, cupric fluoborate electroforming solution；Process time is no less than 60min；When the described eletroforming Between should be controlled in 2~10A/dm with the product of current density2；(4) modulus：Waxed core model after the completion of electroforming is heated in an oven, after wax-pattern all melts loss, then in cleaning agent In cleaned；(5) super-hydrophobic processing：The electroforming cylindrical-array that step (4) obtains is put into the ethanol solution of low-surface-energy material and is carried out Modification dries after taking-up and can be obtained super-hydrophobic cylinder display；The mass fraction of low-surface-energy material ethanol solution is more than 0.1%, the modification time is not less than 30min.
- The electrocasting method of super-hydrophobic columnar arrays 2. a kind of processing drop pie according to claim 1 bounces, feature It is, the core model material is one or more mixing in paraffin, beeswax, gypsum, photoresist.
- The electrocasting method of super-hydrophobic columnar arrays 3. a kind of processing drop pie according to claim 1 or 2 bounces, it is special Sign is that the low-surface-energy material is one or more in silicon fluoride, stearic acid, palmitic acid, lauric acid, myristic acid Mixing.
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Cited By (4)
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| CN110028037A (en) * | 2019-05-07 | 2019-07-19 | 大连理工大学 | A kind of duplication processing technology of super-hydrophobic hemispherical array |
| CN111575748A (en) * | 2020-05-07 | 2020-08-25 | 岭南师范学院 | Electroforming method based on 3D printing rapid molding |
| CN111958958A (en) * | 2020-08-27 | 2020-11-20 | 电子科技大学 | Super-hydrophobic food packaging material and preparation mold and preparation method thereof |
| US11530488B2 (en) * | 2020-12-18 | 2022-12-20 | Ryan Neily | Copper mold for gloves |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028037A (en) * | 2019-05-07 | 2019-07-19 | 大连理工大学 | A kind of duplication processing technology of super-hydrophobic hemispherical array |
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| CN111575748A (en) * | 2020-05-07 | 2020-08-25 | 岭南师范学院 | Electroforming method based on 3D printing rapid molding |
| CN111958958A (en) * | 2020-08-27 | 2020-11-20 | 电子科技大学 | Super-hydrophobic food packaging material and preparation mold and preparation method thereof |
| US11530488B2 (en) * | 2020-12-18 | 2022-12-20 | Ryan Neily | Copper mold for gloves |
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Application publication date: 20180824 |