CN106182725B - A kind of method that method of molding prepares polymer super-hydrophobic surface micro-nano structure - Google Patents
A kind of method that method of molding prepares polymer super-hydrophobic surface micro-nano structure Download PDFInfo
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- CN106182725B CN106182725B CN201610534244.7A CN201610534244A CN106182725B CN 106182725 B CN106182725 B CN 106182725B CN 201610534244 A CN201610534244 A CN 201610534244A CN 106182725 B CN106182725 B CN 106182725B
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- micro
- electroforming
- nano structure
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/002—Component parts, details or accessories; Auxiliary operations
Abstract
The present invention relates to a kind of method that method of molding prepares polymer super-hydrophobic surface micro-nano structure, including：The metallic substrates of deoiling are made into electroforming cathode, nickel plate connects power supply as anode, the Ni-based electroforming solution that passing to Dispersed precipitate between the anode and cathode has non-conductive hard micro-nano particle ball forms electroforming system, and energization makes hard micro-nano particle ball and nickel ion be co-deposited to form Ni-based disperse composite electroforming deposit in metal substrate surface；The metallic substrates for having electroformed layer will be deposited to be electrolysed as anode, remove electroforming layer surface last layer nickel metal so that hard micro-nano particle ball itself is as micro-bulge structure；Workpiece taking-up Jing Guo Electrolyzed Processing deionized water is cleaned only as mold, thermoplastic polymer is heated to more than glass transition temperature, is replicated to obtain the polymer parts with super hydrophobic surface micro-nano structure with the method for hot padding；The carrying tablet that part and drop have silicon fluoride is collectively disposed in closed container and is toasted, metal surface is made to reach ultra-hydrophobicity.
Description
Technical field
The present invention relates to a kind of method that method of molding prepares polymer super-hydrophobic surface micro-nano structure, for changing polymer
Surface wettability makes it have superhydrophobic characteristic.Suitable for the preparation of the super hydrophobic surface of three-dimensional structure complexity, manufacturing cost
It is low, it easily realizes, belongs to Surface Engineering field.
Background technology
It is the phenomenon that solid interface is changed into solid-liquid interface by solid-air interface to soak (Wetting).And wetability
(wettability) refer to ability or tendentiousness that a kind of liquid is sprawled in a kind of surface of solids.Wetability is that there are natures
In universal phenomenon, such as rainwater fall after lotus leaf surface form spherical drop and the phenomenon that tumble and lotus leaf " go out mud and
Do not contaminate " self_cleaning effect, as super-hydrophobic phenomenon.In addition the foot of many animals and plants such as water skipper, butterfly wing, Rice Leaf
Deng, it may have ultra-hydrophobicity.Research shows that superhydrophobic characteristic possessed by all these surfaces is due to micro-nano coarse knot
What structure and low-surface energy substance cooperatively formed.
Wetability is also simultaneously material science and the importance in Surface Engineering field, in daily life, industrial production, agriculture
Many of industry production important application.The so-called super-hydrophobic static contact angle for referring to water droplet in the surface of solids is more than 150 °.At present,
For a large amount of document it has been reported that artificial bionic super hydrophobic surface, these materials are anti-icing in self-cleaning surface, antifog, anti-pollution,
Anticorrosion is widely used in fluid drag-reduction.Polymer material is widely applied in engineering, and using face is extremely extensive, however
The antipollution Corrosion Protection of polymer is poor, therefore prepares superhydrophobic characteristic surface on polymer and be of great significance.
The prior art has the following disadvantages：(1) existing template mainly has biological template method, porous anodic aluminium oxide
Template and aluminium sheet erodent template method etc., they have limitation, and mold on the fine mold for preparing three-dimensional structure complexity
Service life is short；(2) laser or plasma etching method can prepare that precision is high, micro-nano nested structure surface of pattern rule,
But the process efficiency is low, obtains super hydrophobic surface and accumulates small, unsuitable extensive manufacture, and equipment is extremely expensive；(3) electrostatic spinning
Method by using micro-/ nano filament in surface construction coarse structure, can large area prepare super hydrophobic material, but prepare super
The controllability and uniformity of hydrophobic material surface micro-structure are poor, wear no resistance, service life is shorter；(4) physically or chemically gas
Phase sedimentation operating process is simple and the binding force of film and matrix is stronger but required expensive, is generally only applicable to one
The preparation of a little special materials.
Invention content
For the above-mentioned prior art the shortcomings that, it is an object of the invention to propose that a kind of method of molding prepares polymer super-hydrophobic
The method of surface micro-nano structure is the improvement of template, can prepare the fine mold of three-dimensional structure complexity, realize recessed
The hardly possible finished surface such as slot, microtrabeculae, curved surface prepares the super-hydrophobic micro-nano structure of large area, and die life is long, is suitble to high-volume
Low cost manufacturing.
According to an aspect of the present invention, propose that a kind of method of molding prepares the side of polymer super-hydrophobic surface micro-nano structure
Method includes the following steps：(1) using by the metallic substrates of deoiling, as electroforming cathode, nickel plate connects power supply as anode,
The Ni-based electroforming solution that passing to Dispersed precipitate between the anode and cathode has non-conductive hard micro-nano particle ball forms electroforming system, leads to
Electricity makes hard micro-nano particle ball and nickel ion in electroforming solution be co-deposited to form Ni-based disperse composite electroforming deposit in metal substrate surface；
(2) metallic substrates for having electroformed layer will be deposited after the completion of electro-deposition to be electrolysed as anode, remove very thin in electroforming layer surface
One layer of nickel metal so that the hard micro-nano particle ball itself of the Dispersed precipitate revealed is as micro-bulge structure；It (3) will be through
The workpiece taking-up for crossing Electrolyzed Processing is cleaned up by the use of deionized water as mold, and thermoplastic polymer is heated to gamma transition temperature
It more than degree, is replicated to obtain the polymer parts with super hydrophobic surface micro-nano structure with the method for hot padding；(4) finally by part
The carrying tablet for having silicon fluoride with drop, which is collectively disposed in closed container toast, makes silicon fluoride pass through suction-operated in piece surface
The low-surface energy substance of one layer of nano thin-layer is formed, finally metal surface is made to reach ultra-hydrophobicity.
According to an aspect of the present invention, metal base material can be the materials such as nickel, copper, iron, aluminium, stainless steel, best
By the use of high-purity nickel as electroforming substrate, it is allowed to stronger with the binding force of cast layer.
According to an aspect of the present invention, the material of hard micro-nano particle ball is high rigidity, dystectic non-conductive particle
(such as silicon carbide, diamond, silica).
According to an aspect of the present invention, the selection of micro-nano particle ball must be consistent with grain size (20~30um), in electroforming
Volume fraction control is in the range of 40~60% in layer, and the too small spacing that can be distributed particle sphere of volume fraction is excessive, volume point
Counting conference influences the formation of cast layer.The grain size and volume fraction of appropriate mix could form super-hydrophobic needed micro-nano structure.
According to an aspect of the present invention, in step (1), the metallic substrates smooth to surfacing, which can be used, fills ethyl alcohol
The supersonic wave cleaning machine of solution is cleaned, and is recycled removal of surfactant oxidation on metal surface layer, is finally used deionized water
Cleaning is placed in drying removal surface moisture in baking oven.
According to an aspect of the present invention, in step (2), suitable surfactant is added in electroforming solution, is made
It is adsorbed in large quantities forms one layer of firm adsorbed film in micro-nano particle ball surface.
According to an aspect of the present invention, in step (4), may be used micro- injection method batch shape it is super-hydrophobic micro-
Micro-nano structure.
Description of the drawings
Fig. 1 is the process flow chart of the present invention；
Fig. 2 is the super hydrophobic surface micro-nano structure figure of the present invention.
Specific embodiment
The embodiment of the present invention is described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end
Same or like label represents the element of same or like function.Embodiment below with reference to attached drawing description is to show
Example property, it is only used for explaining the present invention, and be not considered as limiting the invention.On the contrary, the embodiment of the present invention includes falling
Enter all changes, modification and the equivalent in the range of the spirit and intension of attached claims.
Such as Fig. 1, the method flow that a kind of method of molding prepares polymer super-hydrophobic surface micro-nano structure is as follows：
The pre-treatment of S1, metallic substrates 1：After impregnating oil removing with hot alkaline solution to metallic substrates 1, with acetone and deionized water
It further rinses, is placed at 120 DEG C of vacuum drying chamber and is dehydrated 15min, to remove impurity so that texture connect jail with metallic substrates 1
Gu.
S2,1 surface dispersion of metallic substrates are composite electroformed：Using nickel plate 2 as anode, metallic substrates 1 are used as cathode, the two
The anode and cathode of power supply 5 are connected respectively to, passing to Dispersed precipitate between the anode and cathode has the nickel of hard micro-nano particle ball 3
Base electroforming solution 4, so as to form electroforming system.Reduction reaction occurs for cathode after energization, makes hard micro-nano particle ball 3 in electroforming solution 4
It is co-deposited to form Ni-based disperse composite electroforming deposit 6 on 1 surface of metallic substrates with nickel ion, cast layer pattern and thickness are by required part
It determines；
In this step, electrical parameter：The square-wave pulse of 0.5~5A/dm2 of current density, 0.5~3KHz of frequency, duty ratio
20~80%, process time (depending on cast layer thickness) etc.；Formulation of electroforming solution：Formulation of electroforming solution：Ni(CH2SO3)2·4H2O—
200~500g/L, NiCl2·6H2O -15~30g/L, H3BO3- 30~45g/L, pH value about 4, about 50 DEG C of temperature etc..
The electrolysis of S3, Ni-based disperse composite electroforming deposit：By the anode and cathode reversal connection of electroforming system after the completion of electro-deposition, make deposition
The metallic substrates 1 for having electroformed layer 6 are electrolysed as anode.Oxidation reaction occurs for anode after energization, removes on 6 surface of electroformed layer
One layer of very thin nickel metal so that the hard micro-nano particle ball 3 of the Dispersed precipitate revealed itself is as micro-bulge 7, i.e., super
Hydrophobic needed micro-nano structure.
In this step, by controlling electrical parameter：10~15A/dm of current density2Direct current, process time is (according to removal
Thickness is determined) the removal thickness (about particle sphere radius size) of control nickel metal layer.Removal thickness, which crosses conference, causes particle sphere easy
It comes off in cast layer, removal thickness is too small, is not easy to form the needed micro-bulge 7 of subsequent handling.
S4, mould-forming super-drainage structure：Using the deionized water of the workpiece taking-up Jing Guo Electrolyzed Processing clean up as
Mold 8.Thermoplastic polymer 9 is heated to more than glass transition temperature, is pressed into mold 8 using mechanical force, and maintain
High temperature, high pressure for a period of time, make thermoplastic polymer 9 be substantially filled in the micro nano structure of mold 8.Object 9 to be polymerized cools down
It after forming, releases stress and is detached from itself and mold 8, so as to obtain that there are the polymer parts of super-hydrophobic micro-nano structure surface
10。
S5, low-surface-energy modification：There is the carrying tablet of silicon fluoride 11 common the polymer parts 10 obtained after demoulding and drop
It is placed in closed container, is then placed in 65 DEG C of baking ovens and toasts 1 hour, put after taking-up to room temperature, complete the preparation of workpiece.It is toasting
In the process, the low-surface energy substance that silicon fluoride 11 will form one layer of nano thin-layer by suction-operated in piece surface, makes polymerization
10 surface of object part reaches ultra-hydrophobicity.
The workpiece for finally preparing completion is as shown in Figure 2.
More preferably, in step sl, the metallic substrates 1 smooth to surfacing can be clear with the ultrasonic wave for filling ethanol solution
Washing machine is cleaned, and is recycled removal of surfactant oxidation on metal surface layer, is finally cleaned with deionized water and be placed in baking oven
Middle drying removal surface moisture.Cause the clean free from admixture non-oxidation layer of 1 surface cleaning of metallic substrates, convenient for what is deposited on its surface
Metal layer has stronger binding force with metallic substrates.
More preferably, in step s 2, suitable surfactant is added in electroforming solution, they can be adsorbed in large quantities
Micro-nano particle ball surface forms one layer of firm adsorbed film, and micro-nano particle pelletizing can be effectively prevent to gather and be aided in electroforming system
Ultrasound or electric and magnetic oscillation stirring can more promote particle suspension effect than simple mechanical stirring.
More preferably, in step s 4, the method batch that micro- injection may be used shapes super-hydrophobic micro-nano structure.
Compared with prior art, advantages of the present invention has：1) method that plating can be used prepares three-dimensional structure
Complicated fine mold is realized and prepares the super-hydrophobic micro-nano structure of large area in the difficult finished surface such as groove, microtrabeculae, curved surface；2) may be used
To obtain the controllable workpiece table of hydrophobicity by selecting variable grain particle size, control particle in the volume fraction of cast layer
Face；3) select hard micro-nano particle ball that can improve die surface wearability for high rigidity, dystectic material, improve mold
Service life；4) high-volume, low cost manufacturing can be realized by preparing super hydrophobic surface micro-nano structure using method of molding.
In the case where not departing from spirit of the invention or necessary characteristic, the present invention can be embodied in other specific forms.It should
The specific embodiment various aspects are considered merely as illustrative and not restrictive.Therefore, scope of the invention such as appended claims
It is shown in range rather than shown as indicated above.All changes fallen in the equivalent meaning and range of claim should be regarded as
It falls in the scope of claim.
Claims (9)
1. a kind of method that method of molding prepares polymer super-hydrophobic surface micro-nano structure, it is characterised in that include the following steps：(1)
Using by the metallic substrates of deoiling, as electroforming cathode, nickel plate connects power supply as anode, leads between the anode and cathode
The Ni-based electroforming solution for having non-conductive hard micro-nano particle ball with Dispersed precipitate is formed electroforming system, and energization makes hard in electroforming solution micro-
It receives particle ball and nickel ion is co-deposited to form Ni-based disperse composite electroforming deposit in metal substrate surface；It (2) will after the completion of electro-deposition
The metallic substrates that depositing has electroformed layer are electrolysed as anode, remove one layer of nickel metal very thin in electroforming layer surface so that
The hard micro-nano particle ball itself of the Dispersed precipitate revealed is as micro-bulge structure；(3) by the workpiece Jing Guo Electrolyzed Processing
Taking-up deionized water is cleaned up as mold, and thermoplastic polymer is heated to more than glass transition temperature, uses hot padding
Method replicate to obtain the polymer parts with super hydrophobic surface micro-nano structure；(4) part and drop finally there is into silicon fluoride
Carrying tablet, which is collectively disposed in closed container toast, makes silicon fluoride pass through suction-operated in piece surface one layer of nanometer thin of formation
The low-surface energy substance of layer, finally makes metal surface reach ultra-hydrophobicity.
2. the method that method of molding as described in claim 1 prepares polymer super-hydrophobic surface micro-nano structure, which is characterized in that institute
Nickel, copper, iron, aluminium, stainless steel material can be selected by stating metallic substrates.
3. the method that method of molding as described in claim 1 prepares polymer super-hydrophobic surface micro-nano structure, which is characterized in that institute
It is preferably high-purity nickel to state metallic substrates.
4. the method that method of molding as described in claim 1 prepares polymer super-hydrophobic surface micro-nano structure, which is characterized in that institute
The material for stating hard micro-nano particle ball is high rigidity, dystectic non-conductive particle.
5. the method that method of molding as described in claim 1 prepares polymer super-hydrophobic surface micro-nano structure, which is characterized in that institute
The material for stating hard micro-nano particle ball is preferably silicon carbide, diamond or silica.
6. the method that method of molding as described in claim 1 prepares polymer super-hydrophobic surface micro-nano structure, which is characterized in that institute
State hard micro-nano particle ball selection and grain size must it is consistent, particle size be 20~30um, the volume fraction in electroformed layer
Control is in the range of 40~60%.
7. the method that method of molding as described in claim 1 prepares polymer super-hydrophobic surface micro-nano structure, which is characterized in that
In step (1), the metallic substrates smooth to surfacing can be used the supersonic wave cleaning machine for filling ethanol solution to clean, then profit
With removal of surfactant oxidation on metal surface layer, finally cleaned with deionized water and be placed in drying removal surface water in baking oven
Point.
8. the method that method of molding as described in claim 1 prepares polymer super-hydrophobic surface micro-nano structure, which is characterized in that
In step (1), suitable surfactant is added in electroforming solution, it is made to adsorb in large quantities and is formed in micro-nano particle ball surface
One layer of firm adsorbed film.
9. the method that method of molding as described in claim 1 prepares polymer super-hydrophobic surface micro-nano structure, which is characterized in that
In step (3), the method batch that micro- injection may be used shapes super-hydrophobic micro-nano structure.
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| CN107573531B (en) | 2017-07-13 | 2020-08-14 | 大连理工大学 | Hot-pressing processing method of large-size super-hydrophobic cylindrical array with liquid drop pie-shaped bouncing |
| CN110028037B (en) * | 2019-05-07 | 2021-08-10 | 大连理工大学 | Copying processing technology of super-hydrophobic hemisphere array |
| CN110684994A (en) * | 2019-09-24 | 2020-01-14 | 李国柱 | Manufacturing method of wide metal template with super-hydrophobic micro-nano surface structure |
| CN112094589B (en) * | 2020-09-21 | 2021-12-14 | 四川大学 | Preparation and application of environment-friendly low-cost super-hydrophobic powder material |
| CN114950921B (en) * | 2022-05-18 | 2023-03-24 | 广东工业大学 | Method for constructing porous micro-nano structure and material with porous micro-nano structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313654A (en) * | 2014-10-13 | 2015-01-28 | 中南大学 | Mold core with copied natural biological super-hydrophobic surface as well as preparation method and application of mold core |
| CN105386090A (en) * | 2015-11-09 | 2016-03-09 | 广东工业大学 | Method for manufacturing ultra-oleophobic metal surface with recessed micropores |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313654A (en) * | 2014-10-13 | 2015-01-28 | 中南大学 | Mold core with copied natural biological super-hydrophobic surface as well as preparation method and application of mold core |
| CN105386090A (en) * | 2015-11-09 | 2016-03-09 | 广东工业大学 | Method for manufacturing ultra-oleophobic metal surface with recessed micropores |
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