CN107574464B - A kind of preparation method with hierarchical structure mushroom-shaped metal column array surface - Google Patents
A kind of preparation method with hierarchical structure mushroom-shaped metal column array surface Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of hierarchical structure mushroom-shaped metal column array surface.The present invention is prepared in metal surface the mushroom-shaped metal column array with micro-nano hierarchical structure using the double-deck polycarbonate membrane with nano-pore and micron openings as template, by electroplating technology.The mushroom-shaped metal column array shows as super-hydrophobicity after surface fluorination.The process flow of method of the invention without expensive instrument and equipment or complexity, simple, economy, the high mechanical strength of surface micro-structure obtained, persistence are strong, can greatly expand the application field on super wetting surface.
Description
Technical field
The present invention relates to field of material preparation more particularly to a kind of with hierarchical structure mushroom-shaped metal column array surface
Preparation method.
Background technique
In recent years, the super hydrophobic surface with the contact angle of water greater than 150 ° caused great concern, because it is certainly
Cleaning material, microfluidic device and biomaterial etc. have extremely important application prospect in many fields.In nature
Certain plants leaf surface, most typically lotus leaf surface, has superhydrophobic property and self-cleaning function (lotus leaf effect).1997
Year, the researchers such as botanist's Bartelot of Univ Bonn Germany are recognized by studying nearly 300 kinds of leaf surface of plant
It for this self-cleaning characteristic is caused jointly by the mastoid process of micrometer structure on rough surface and the wax material of surface hydrophobicity
's.2002, the discovery such as river thunder in the mastoid process of lotus leaf surface micrometer structure there is also nanostructure, this micrometer structure with receive
The hierarchical structure that rice structure combines is to cause the basic reason of super hydrophobic surface.
Many researchers are attempted to use 3D printing, using the anodic alumina films with branched structure as template, with micron ball and
Nanosphere is to cover an edition deep etching, first constructs micrometer structure again on its surface by selective wet chemical etching, plasma etching, from group
The multiple technologies such as the technologies such as dress preparation nanostructure, raspberry shape particle prepare stratum's knot that micrometer structure is combined with nanostructure
Structure surface.But existing method is related to the process flow of expensive instrument and equipment or complexity more, it is difficult to super for large area
The preparation on surface, while super wetting surface micro-structure bad mechanical strength prepared at present are soaked, service life is shorter, vulnerable to outer
Boundary's factor such as light, temperature etc. influences, and is not able to satisfy the requirement of long-time service.Therefore develop a kind of preparation process it is simple, it is economical,
The high mechanical strength of surface micro-structure, environmental-friendly preparation process can greatly expand the application field on super wetting surface.
Summary of the invention
Regarding the issue above, the present invention provides a kind of preparation process is simple, the machine of economy, surface micro-structure
The preparation method with hierarchical structure mushroom-shaped metal column array surface that tool intensity is high, persistence is strong.
The technical solution of the present invention is as follows:
A kind of preparation method with hierarchical structure mushroom-shaped metal column array surface the following steps are included:
1) substrate with flat metal surface is provided；
2) the polycarbonate perforated membrane with micron order aperture is successively covered on the metal surface Yu Suoshu and there is nanoscale
The polycarbonate perforated membrane in aperture, the polycarbonate perforated membrane in the micron order aperture and the polycarbonate in nanoscale aperture are porous
Residual air forms hollow layer between film；
3) electroplating technology is used, is to cover version, Yu Suoshu with the double-deck polycarbonate porous membrane structure using workpiece as cathode
Layer on surface of metal galavanic growth metal forms micron column within micron openings, and overflows micron openings and expand outwardly to be formed in hollow layer
Bacterium lid-like then forms nano-pillar in the nano-pore on the bacterium lid-like, so that being formed has hierarchical structure mushroom
Shape metal column array；
4) version is covered using organic solvent dissolution removal polycarbonate, after cleaning-drying, obtained with hierarchical structure mushroom-shaped
Metal column array surface.
Optionally, the porous membrane aperture of polycarbonate in the micron order aperture is 2~50 μm, with a thickness of 5~50 μm.
Optionally, the porous membrane aperture of polycarbonate in the nanoscale aperture is 50~800nm, with a thickness of 2~50 μm.
Optionally, in step 3), the plating metal is at least one of silver, copper, nickel, iron.
Optionally, step 1) is specifically to be sequentially depositing titanium layer in monocrystalline silicon sheet surface and layer gold is formed described has smooth gold
The substrate of metal surface.
Optionally, the electric current of the plating is 5~25mA, and electroplating time is 10~50 minutes.
It optionally, further include that the structure for forming step 4) immerses ten that the mass fraction that hydrolyzes in advance is 0.5~2wt%
In trifluoro octyltri-ethoxysilane ethanol solution, taken out after impregnating 0.5~2 hour at room temperature, then in 100~140 DEG C of heat
Processing 0.5~2 hour after be cooled to room temperature with carry out it is fluorinated modified after for super hydrophobic surface.
The hierarchical structure mushroom-shaped metal column array surface that the present invention is prepared according to above-mentioned preparation process, water droplet is in surface fluorine
Hierarchical structure mushroom-shaped metal column array surface after change reaches super-hydrophobic effect.
The process flow of method of the invention without expensive instrument and equipment or complexity, simple, economy, surface obtained are micro-
High mechanical strength, the persistence of structure are strong, can greatly expand the application field on super wetting surface.
Detailed description of the invention
Fig. 1 is the preparation process schematic diagram with hierarchical structure mushroom-shaped metal column array surface.
Fig. 2 is the schematic illustration of galavanic growth mushroom-shaped metal column.
Fig. 3 is that the scanning electron of hierarchical structure mushroom-shaped silver metal column array surface prepared by the embodiment of the present invention 1 is aobvious
Micro mirror photo.
Fig. 4 is that the scanning electron of hierarchical structure mushroom-shaped copper metal column array surface prepared by the embodiment of the present invention 2 is aobvious
Micro mirror photo.
Fig. 5 is to connect after hierarchical structure mushroom-shaped silver metal column array surface prepared by the embodiment of the present invention 1 is fluorinated with water
Feeler test result.
Fig. 6 is to connect after hierarchical structure mushroom-shaped copper metal column array surface prepared by the embodiment of the present invention 2 is fluorinated with water
Feeler test result.
Specific embodiment
With reference to Fig. 1, hierarchical structure mushroom-shaped metal column array of the invention the preparation method comprises the following steps:
1) substrate with flat metal surface is provided；It specifically can be in being sequentially depositing titanium layer and gold on monocrystalline silicon piece
Layer, the titanium layer with a thickness of 50~200nm, the layer gold with a thickness of 10~50nm；
2) the polycarbonate perforated membrane with micron order aperture is successively covered on Yu Suoshu metal layer and there is nano grade pore
The polycarbonate perforated membrane of diameter, the polycarbonate perforated membrane in the micron order aperture and the polycarbonate perforated membrane in nanoscale aperture
Between residual air formed hollow layer；The porous membrane aperture of polycarbonate in the micron order aperture is 2~50 μm, with a thickness of 5~
50μm；The porous membrane aperture of polycarbonate in the nanoscale aperture is 50~800nm, with a thickness of 2~50 μm；
3) electroplating technology is used, is to cover version, Yu Suoshu with the double-deck polycarbonate porous membrane structure using workpiece as cathode
Layer on surface of metal galavanic growth metal forms micron column within micron openings, and overflows micron openings and expand outwardly to be formed in hollow layer
Bacterium lid-like then forms nano-pillar in the nano-pore on the bacterium lid-like, so that being formed has hierarchical structure mushroom
Shape metal column array；The thickness of the bacterium lid-like depends on the thickness of hollow layer, specially nanoscale to micron order；It is described
Plating metal is at least one of silver, copper, nickel, iron；The electric current of the plating is 5~25mA, and electroplating time is 10~50 points
Clock；
4) version is covered using organic solvent dissolution removal polycarbonate, and after being cleaned and dried using ethyl alcohol and deionized water, obtained
To with hierarchical structure mushroom-shaped metal column array surface.
It is to cover version with the double-deck polycarbonate porous membrane structure with reference to Fig. 2, when duplicature superposition, centre can nubbin
Air forms hollow layer.In galavanic growth metal process, when the polycarbonate that micron pillar height degree is more than micron order aperture is porous
When film thickness, the current density at micron column edge and center is big, is preferred growth region, so still can outwardly and upwardly expand
The shape of similar mushroom is integrally formed with micron column to form bacterium lid-like in hollow layer by Zhang Shengchang, at the top of cap
When touching the polycarbonate perforated membrane bottom in nanoscale aperture, nano-pore growth is continued on, thus forms hierarchical structure
Mushroom-shaped metal column array.
Above structure is immersed to the tridecafluoro-n-octyltriethoxysilane that the mass fraction hydrolyzed in advance is 0.5~2wt%
In ethanol solution, taken out after impregnating 0.5~2 hour at room temperature, it is cooling after being then heat-treated 0.5~2 hour at 100~140 DEG C
To room temperature, there is ultra-hydrophobicity after perfluorinated.
Embodiment 1
One layer of 100nm thickness titanium film and 20nm thick gold membrane are sequentially depositing on monocrystalline silicon piece, by the poly- carbon with 12 μm of apertures
Acid esters perforated membrane (with a thickness of 14 μm) and the polycarbonate perforated membrane (with a thickness of 20 μm) in the aperture 400nm are successively covered in silicon base
Surface.It takes appropriate plating solution for silver-plating to be added in electroplating bath, anode platinum electrode and reference electrode is immersed in electroplate liquid, be yin with workpiece
Pole is to cover version with the double-deck polycarbonate membrane, and using constant current silver electroplating technology, electric current 10mA, electroplating time is 35 minutes,
The growth of its electroplating surface has hierarchical structure mushroom-shaped silver metal column array.Galvanostat is closed after reaching setting time, is taken out
It is coated with the sample finished.Sample is immersed in removal polycarbonate perforated membrane in chloroform, and clear with ethyl alcohol and deionized water
Surface is washed, kept dry is finally obtained with hierarchical structure mushroom-shaped silver metal column array surface.Its scanning electron microscope form is shown in figure
3, the mushroom-shaped metal column array with hierarchical structure is formd as seen from the figure, and the thickness of its bacterium lid-like is about 4 μm,
Diameter range is about 36 μm.It is molten that said sample is immersed to the 1wt.% tridecafluoro-n-octyltriethoxysilane ethyl alcohol hydrolyzed in advance
It in liquid, is taken out after impregnating 1 hour at room temperature, measurement is cooled to room temperature after being then heat-treated 1 hour at 120 DEG C of baking oven, and it connects with water
Feeler.Fig. 5 is seen with the contact angle of water, is 151.5 °.
Embodiment 2
One layer of 100nm thickness titanium film and 20nm thick gold membrane are sequentially depositing on monocrystalline silicon piece, by the poly- carbonic acid with 5 μm of apertures
Ester perforated membrane (with a thickness of 10 μm) and the polycarbonate perforated membrane (with a thickness of 10 μm) in the aperture 500nm are successively covered in silicon base table
Face.It takes appropriate copper electroplating liquid to be added in electroplating bath, anode platinum electrode and reference electrode is immersed in electroplate liquid, be yin with workpiece
Pole is to cover version with the double-deck polycarbonate membrane, and using constant potential copper electroplating technology, electric current 19mA, electroplating time is 20 minutes,
The growth of its electroplating surface has hierarchical structure mushroom-shaped copper metal column array.Galvanostat is closed after reaching setting time, is taken out
It is coated with the sample finished.Sample is immersed in removal polycarbonate perforated membrane in chloroform, and clear with ethyl alcohol and deionized water
Surface is washed, kept dry is finally obtained with hierarchical structure mushroom-shaped copper metal column array surface.Its scanning electron microscope form is shown in figure
4, the mushroom-shaped metal column array with hierarchical structure is formd as seen from the figure, and the thickness of its bacterium lid-like is about 4.2 μ
M, diameter range are about 24 μm.Said sample is immersed to the 1wt.% tridecafluoro-n-octyltriethoxysilane ethyl alcohol hydrolyzed in advance
It in solution, is taken out after impregnating 1 hour at room temperature, is cooled to room temperature after being then heat-treated 1 hour at 120 DEG C of baking oven and measures itself and water
Contact angle.Fig. 6 is seen with the contact angle of water, is 150 °.
Above-described embodiment is only used to further illustrate that one kind of the invention has hierarchical structure mushroom-shaped metal column array table
The preparation method in face, but the invention is not limited to embodiments, according to the technical essence of the invention to above embodiments institute
Any simple modification, equivalent change and modification of work, fall within the scope of protection of technical solution of the present invention.
Claims (7)
1. a kind of preparation method with hierarchical structure mushroom-shaped metal column array surface, it is characterised in that the following steps are included:
1) substrate with flat metal surface is provided；
2) the polycarbonate perforated membrane with micron order aperture is successively covered on the metal surface Yu Suoshu and there is nanoscale aperture
Polycarbonate perforated membrane, the polycarbonate perforated membrane in the polycarbonate perforated membrane in the micron order aperture and nanoscale aperture it
Between residual air formed hollow layer；
3) electroplating technology is used, is to cover version, the metal surface Yu Suoshu with the double-deck polycarbonate porous membrane structure using workpiece as cathode
Galavanic growth metal forms micron column within micron openings, and overflows micron openings and expand outwardly to form cap shape knot in hollow layer
Structure then forms nano-pillar in the nano-pore on the bacterium lid-like, so that being formed has hierarchical structure mushroom-shaped metal column
Array；
4) version is covered using organic solvent dissolution removal polycarbonate, after cleaning-drying, obtained with hierarchical structure mushroom-shaped metal
Column array surface.
2. preparation method according to claim 1, it is characterised in that: step 1) is specifically successively to sink in monocrystalline silicon sheet surface
Product titanium layer and layer gold form the substrate with flat metal surface.
3. preparation method according to claim 1, it is characterised in that: the polycarbonate in micron order aperture described in step 2 is more
Hole membrane aperture is 2 ~ 50 μm, with a thickness of 5 ~ 50 μm.
4. preparation method according to claim 1, it is characterised in that: the polycarbonate in nanoscale aperture described in step 2 is more
Hole membrane aperture is 50 ~ 800nm, with a thickness of 2 ~ 50 μm.
5. preparation method according to claim 1, it is characterised in that: in step 3), the plating metal be silver, copper, nickel,
At least one of iron.
6. preparation method according to claim 1, it is characterised in that: in step 3), the electric current of the plating is 5 ~ 25mA,
Electroplating time is 10 ~ 50 minutes.
7. preparation method according to claim 1, it is characterised in that: further include that the structure for forming step 4) immerses in advance
The mass fraction of hydrolysis is that it is small to impregnate 0.5 ~ 2 at room temperature in the tridecafluoro-n-octyltriethoxysilane ethanol solution of 0.5 ~ 2wt%
When after take out, be cooled to room temperature after being then heat-treated 0.5 ~ 2 hour at 100 ~ 140 DEG C with carry out it is fluorinated modified after for super-hydrophobic table
Face.
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