CN107574464A - 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 method 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.Technological process of the method for the present invention without expensive instrument and equipment or complexity, high mechanical strength, the persistence of simple, economic, obtained surface micro-structure 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 it is a kind of with hierarchical structure mushroom-shaped metal column array surface
Preparation method.
Background technology
In recent years, great concern was caused with super hydrophobic surface of the contact angle of water more than 150 °, 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 researcher such as botanist's Bartelot of Univ Bonn Germany is recognized by studying nearly 300 kinds of leaf surface of plant
For this self-cleaning characteristic caused jointly by the mastoid process of micrometer structure on rough surface and the wax material of surface hydrophobicity
's.2002, river thunder etc. found nanostructured in the mastoid process of lotus leaf surface micrometer structure also be present, and this micrometer structure is with receiving
The hierarchical structure that rice structure is combined is to cause the basic reason of super hydrophobic surface.
Many researchers attempt use 3D printing, using the anodic alumina films with branched structure as template, with micron ball with
Nanosphere to cover an edition deep etching, first build micrometer structure again its surface by selective wet chemical etching, plasma etching, from group
The technologies such as dress prepare the multiple technologies such as nanostructured, raspberry shape particle and prepare stratum's knot that micrometer structure is combined with nanostructured
Structure surface.But existing method is related to the instrument and equipment of costliness or the technological process of complexity more, it is difficult to surpasses 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, easily by outer
Boundary's factor such as light, temperature etc. influence, it is impossible to meet the requirement of long-term use.Therefore develop a kind of preparation technology it is simple, it is economical,
The high mechanical strength of surface micro-structure, environment-friendly preparation technology, it can greatly expand the application field on super wetting surface.
The content of the invention
Regarding the issue above, the present invention provides a kind of preparation technology 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 scheme is that：
A kind of preparation method with hierarchical structure mushroom-shaped metal column array surface comprises the following steps：
1) substrate with flat metal surface is provided；
2) in makrolon perforated membrane with micron order aperture being covered on the metal surface successively and with nanoscale
The makrolon perforated membrane in aperture, the makrolon perforated membrane in the micron order aperture and the makrolon in nanoscale aperture are porous
Residual air forms hollow layer between film；
3) electroplating technology is used, using workpiece as negative electrode, using the double-deck makrolon porous membrane structure as version is covered, in described
Layer on surface of metal galavanic growth metal forms micron post within micron openings, and overflows micron openings and expand outwardly to be formed in hollow layer
Bacterium lid-like, and nano-pillar is formed in the nano-pore on the cap shape structure, so as to be formed with hierarchical structure mushroom
Shape metal column array；
4) makrolon is removed using organic solvent dissolving and covers version, after cleaning-drying, obtained with hierarchical structure mushroom-shaped
Metal column array surface.
Optionally, the porous membrane aperture of makrolon in the micron order aperture is 2~50 μm, and thickness is 5~50 μm.
Optionally, the porous membrane aperture of makrolon in the nanoscale aperture is 50~800nm, and thickness is 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 forms and 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.
Optionally, in addition to by step 4) it is the ten of 0.5~2wt% that the structure formed, which immerses the mass fraction hydrolyzed in advance,
In trifluoro octyltri-ethoxysilane ethanol solution, taken out after soaking 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 technology, water droplet is in surface fluorine
Hierarchical structure mushroom-shaped metal column array surface after change reaches super-hydrophobic effect.
Technological process of the method for the present invention without expensive instrument and equipment or complexity, simple, economic, obtained surface are micro-
High mechanical strength, the persistence of structure are strong, can greatly expand the application field on super wetting surface.
Brief description of the drawings
Fig. 1 is the preparation process schematic diagram with hierarchical structure mushroom-shaped metal column array surface.
Fig. 2 is the principle schematic of galavanic growth mushroom-shaped metal column.
Fig. 3 is that the scanning electron of the hierarchical structure mushroom-shaped silver metal post array surface prepared by the embodiment of the present invention 1 shows
Micro mirror photo.
Fig. 4 is that the scanning electron of the hierarchical structure mushroom-shaped copper metal post array surface prepared by the embodiment of the present invention 2 shows
Micro mirror photo.
Fig. 5 is to be connect after the hierarchical structure mushroom-shaped silver metal post array surface prepared by the embodiment of the present invention 1 is fluorinated with water
Feeler test result.
Fig. 6 is to be connect after the hierarchical structure mushroom-shaped copper metal post array surface prepared by the embodiment of the present invention 2 is fluorinated with water
Feeler test result.
Embodiment
With reference to figure 1, the preparation method of hierarchical structure mushroom-shaped metal column array of the invention is：
1) substrate with flat metal surface is provided；Can be specifically in being sequentially depositing titanium layer and gold on monocrystalline silicon piece
Layer, the thickness of the titanium layer is 50~200nm, and the thickness of the layer gold is 10~50nm；
2) in makrolon perforated membrane with micron order aperture being covered on the metal level successively and with nano grade pore
The makrolon perforated membrane in footpath, the makrolon perforated membrane in the micron order aperture and the makrolon perforated membrane in nanoscale aperture
Between residual air formed hollow layer；The porous membrane aperture of makrolon in the micron order aperture be 2~50 μm, thickness be 5~
50μm；The porous membrane aperture of makrolon in the nanoscale aperture is 50~800nm, and thickness is 2~50 μm；
3) electroplating technology is used, using workpiece as negative electrode, using the double-deck makrolon porous membrane structure as version is covered, in described
Layer on surface of metal galavanic growth metal forms micron post within micron openings, and overflows micron openings and expand outwardly to be formed in hollow layer
Bacterium lid-like, and nano-pillar is formed in the nano-pore on the cap shape structure, so as to be formed with 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) makrolon is removed using organic solvent dissolving and covers version, and after being cleaned and dried using ethanol and deionized water, obtained
To with hierarchical structure mushroom-shaped metal column array surface.
With reference to figure 2, using double-deck makrolon porous membrane structure as version is covered, when duplicature is superimposed, centre can nubbin
Air forms hollow layer.In galavanic growth metal process, the makrolon that micron order aperture is exceeded when micron pillar height degree is porous
During film thickness, the current density at micron post edge and center is big, is preferred growth region, so still can outwardly and upwardly expand
Zhang Shengchang, so as to form bacterium lid-like in hollow layer, the shape of similar mushroom is integrally formed with micron post, at the top of cap
When touching the makrolon perforated membrane bottom in nanoscale aperture, nano-pore growth is continued on, thus forms hierarchical structure
Mushroom-shaped metal column array.
Said structure is immersed to the tridecafluoro-n-octyltriethoxysilane that the mass fraction hydrolyzed in advance is 0.5~2wt%
In ethanol solution, take out after soaking 0.5~2 hour at room temperature, cooled down 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 membranes are sequentially depositing on monocrystalline silicon piece, by the poly- carbon with 12 μm of apertures
Acid esters perforated membrane (thickness is 14 μm) and the makrolon perforated membrane (thickness is 20 μm) in 400nm apertures are covered in silicon base successively
Surface.Take appropriate plating solution for silver-plating to add in electroplating bath, anode platinum electrode and reference electrode are immersed in electroplate liquid, using workpiece as the moon
Pole, using double-deck polycarbonate membrane as version is covered, 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 post array.Galvanostat is closed after reaching setting time, is taken out
It is coated with the sample finished.Sample is immersed in removal makrolon perforated membrane in chloroform, and it is clear with ethanol and deionized water
Surface is washed, kept dry, is finally given with hierarchical structure mushroom-shaped silver metal post array surface.Its ESEM 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 ethanol hydrolyzed in advance
In liquid, taken out after soaking 1 hour at room temperature, room temperature measuring is then cooled to after the heat treatment 1 hour of 120 DEG C of baking oven, and it connects with water
Feeler.See Fig. 5 with the contact angle of water, be 151.5 °.
Embodiment 2
One layer of 100nm thickness titanium film and 20nm thick gold membranes are sequentially depositing on monocrystalline silicon piece, by the poly- carbonic acid with 5 μm of apertures
Ester perforated membrane (thickness is 10 μm) and the makrolon perforated membrane (thickness is 10 μm) in 500nm apertures are covered in silicon base table successively
Face.Take appropriate copper electroplating liquid to add in electroplating bath, anode platinum electrode and reference electrode are immersed in electroplate liquid, using workpiece as the moon
Pole, using double-deck polycarbonate membrane as version is covered, 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 post array.Galvanostat is closed after reaching setting time, is taken out
It is coated with the sample finished.Sample is immersed in removal makrolon perforated membrane in chloroform, and it is clear with ethanol and deionized water
Surface is washed, kept dry, is finally given with hierarchical structure mushroom-shaped copper metal post array surface.Its ESEM 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 ethanol hydrolyzed in advance
In solution, taken out after soaking 1 hour at room temperature, room temperature measuring itself and water is then cooled to after the heat treatment 1 hour of 120 DEG C of baking oven
Contact angle.See Fig. 6 with the contact angle of water, be 150 °.
Above-described embodiment is only used for further illustrating that one kind of the present invention has hierarchical structure mushroom-shaped metal column array table
The preparation method in face, but the invention is not limited in embodiment, every technical spirit according to the present invention is to above example institute
Any simple modification, equivalent change and modification made, each falls within the protection domain 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 comprise the following steps：
1) substrate with flat metal surface is provided；
2) in makrolon perforated membrane with micron order aperture being covered on the metal surface successively and with nanoscale aperture
Makrolon perforated membrane, the makrolon perforated membrane in the micron order aperture and the makrolon perforated membrane in nanoscale aperture it
Between residual air formed hollow layer；
3) electroplating technology is used, using workpiece as negative electrode, using the double-deck makrolon porous membrane structure as version is covered, in the metal
Layer surface galavanic growth metal forms micron post within micron openings, and overflows micron openings and expand outwardly to form cap in hollow layer
Shape structure, and nano-pillar is formed in the nano-pore on the cap shape structure, so as to be formed with hierarchical structure mushroom-shaped gold
Belong to post array；
4) makrolon is removed using organic solvent dissolving and covers version, after cleaning-drying, obtained with hierarchical structure mushroom-shaped metal
Post array surface.
2. preparation method according to claim 1, it is characterised in that：Step 1) is specifically to be sunk successively 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 makrolon in step 2) the micron order aperture is more
Pore membrane aperture is 2~50 μm, and thickness is 5~50 μm.
4. preparation method according to claim 1, it is characterised in that：The makrolon in step 2) the nanoscale aperture is more
Pore membrane aperture is 50~800nm, and thickness is 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 for 5~
25mA, electroplating time are 10~50 minutes.
7. preparation method according to claim 1, it is characterised in that：The structure for also including forming step 4) immerses advance
The mass fraction of hydrolysis is in 0.5~2wt% tridecafluoro-n-octyltriethoxysilane ethanol solution, soaks 0.5~2 at room temperature
Taken out after hour, it is fluorinated modified rear to be super thin to carry out to be cooled to room temperature after being then heat-treated 0.5~2 hour at 100~140 DEG C
Water surface.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109518130A (en) * | 2018-12-29 | 2019-03-26 | 深圳先进技术研究院 | Microporous metal membrane and preparation method |
| CN112661102A (en) * | 2020-11-30 | 2021-04-16 | 上海联影医疗科技股份有限公司 | Surface structure, surface structure preparation method and medical equipment |
| CN115125572A (en) * | 2022-06-22 | 2022-09-30 | 北京航空航天大学 | Preparation method and application of mushroom-shaped array electrode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200815278A (en) * | 2006-06-28 | 2008-04-01 | Univ Northwestern | DPN generated hole nanoarrays |
| CN101319407A (en) * | 2008-06-25 | 2008-12-10 | 北京理工大学 | Preparation method of metallic oxide nanometer granular nano-array material |
| CN102612424A (en) * | 2010-03-19 | 2012-07-25 | 学校法人早稻田大学 | Mold manufacture method and mold formed by said method |
| CN103046088A (en) * | 2012-12-20 | 2013-04-17 | 华南理工大学 | Micro-nano composite porous copper surface structure and preparation method and device thereof |
| CN105220185A (en) * | 2015-10-29 | 2016-01-06 | 广东工业大学 | A kind of preparation method of super oleophobic micro-pillar array Surface Texture |
-
2017
- 2017-08-31 CN CN201710771070.0A patent/CN107574464B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200815278A (en) * | 2006-06-28 | 2008-04-01 | Univ Northwestern | DPN generated hole nanoarrays |
| CN101319407A (en) * | 2008-06-25 | 2008-12-10 | 北京理工大学 | Preparation method of metallic oxide nanometer granular nano-array material |
| CN102612424A (en) * | 2010-03-19 | 2012-07-25 | 学校法人早稻田大学 | Mold manufacture method and mold formed by said method |
| CN103046088A (en) * | 2012-12-20 | 2013-04-17 | 华南理工大学 | Micro-nano composite porous copper surface structure and preparation method and device thereof |
| CN105220185A (en) * | 2015-10-29 | 2016-01-06 | 广东工业大学 | A kind of preparation method of super oleophobic micro-pillar array Surface Texture |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109518130A (en) * | 2018-12-29 | 2019-03-26 | 深圳先进技术研究院 | Microporous metal membrane and preparation method |
| CN112661102A (en) * | 2020-11-30 | 2021-04-16 | 上海联影医疗科技股份有限公司 | Surface structure, surface structure preparation method and medical equipment |
| CN115125572A (en) * | 2022-06-22 | 2022-09-30 | 北京航空航天大学 | Preparation method and application of mushroom-shaped array electrode |
| CN115125572B (en) * | 2022-06-22 | 2023-12-19 | 北京航空航天大学 | Preparation method and application of mushroom-shaped array electrode |
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