CN108466015A - A kind of super-amphiphobic metal surface and preparation method thereof of nanostructure distributed in three dimensions - Google Patents
A kind of super-amphiphobic metal surface and preparation method thereof of nanostructure distributed in three dimensions Download PDFInfo
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- CN108466015A CN108466015A CN201810316726.4A CN201810316726A CN108466015A CN 108466015 A CN108466015 A CN 108466015A CN 201810316726 A CN201810316726 A CN 201810316726A CN 108466015 A CN108466015 A CN 108466015A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/361—Removing material for deburring or mechanical trimming
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/60—Preliminary treatment
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
Abstract
A kind of super-amphiphobic metal surface and preparation method thereof of nanostructure distributed in three dimensions, belongs to technical field of function materials.The super-double-hydrophobic surface is that three dimensional micron array structure is distributed on metal base, and array surface is distributed the nanometer grass-like structure that flexible, slim nanometer silk fabric striped cell is wound mutually.The method forms three dimensional micron structure first with ultrafast laser patterning ablation metallic substrate surface, then it is aoxidized by chemical bath and forms nanometer grass-like structure in three dimensional micron body structure surface, surface modification treatment is carried out with perfluoro decyl trimethoxy silane again, realizes super-hydrophobic superoleophobic function.The super-double-hydrophobic surface has excellent durability, preparation method is simple and practicable, rapidly and efficiently, can large area prepare, self-cleaning performance can be kept for a long time under a variety of external environments such as outdoor, be with a wide range of applications in fields such as national defence, industrial production, daily lifes.
Description
Technical field
The present invention relates to a kind of super-amphiphobic (while super-hydrophobic and superoleophobic) surface having good durability and its preparations
Method, and in particular to a kind of durability super-amphiphobic metal surface of nanostructure distributed in three dimensions and its laser, chemically composited preparation
Method belongs to technical field of function materials.
Background technology
Surface with special wellability is concerned because of its interesting phenomenon with due to being widely applied foreground all the time.
In these special wellability surfaces, super hydrophobic surface is the field of classics the most, has been studied many decades.Currently, super thin
The mechanism of water surface behind has been obtained for more mature research and illustrates, i.e., the surface composition and micro-nano of low free energy are compound
Surface texture be two key factors for realizing super-hydrophobicity and self-cleaning function.Recently, another special wellability table
Face, i.e. super-double-hydrophobic surface have attracted the extensive concern of researcher.Super-double-hydrophobic surface can realize the super thin performance to water and oil simultaneously,
I.e. contact angle is more than 150 ° while roll angle is less than 10 °.Super-double-hydrophobic surface national defence, industrial production, daily life each neck
There is a foreground that is more widely applied in domain, such as oil resistant coating, automatically cleaning, water-oil separating, oil droplet operation, anticorrosive, therefore
Preparation in recent years in relation to artificial super hydrophobic surface has attracted scientific research and industrial circle more and more to pay close attention to.
Since the surface tension of oil is much smaller than water, the realization difficulty of super-double-hydrophobic surface improves very compared with super hydrophobic surface
It is more, only lean on the surface composition of low free energy and conventional micro-nano surface to cannot achieve good superoleophobic performance.Research
It needs to introduce the structure with re-entrant angle feature it was found that preparing super-double-hydrophobic surface, because in reentrant features, along solid-liquid contact line
Surface tension caused by pressure direction it is upward, balance downward laplace pressure and oil droplet gravity so as to play
Effect；Coordinate micron and nanometer composite structure and low free energy ingredient again, air layer will be formed between oil droplet and micro nano structure, from
And reach Cassie states, realize oil droplet in body structure surface free rolling characteristic, i.e. self-cleaning function.Therefore, there is re-entrant angle
The structure of feature is to realizing that ultra-amphosphobic can have key effect.
In the super-double-hydrophobic surface with re-entrant angle feature delivered at present, the design of reentrant features is broadly divided into following two
Kind thinking：The first mentality of designing is to prepare the regular micrometer structure with re-entrant angle feature, including cantilever micrometer structure, mushroom
Shape micrometer structure, inverted trapezoidal micrometer structure etc..These structures provide the re-entrant angle feature of micro-meter scale, can realize excellent super double
Dredge performance, as patent CN104768868A, patent CN102180016A, patent CN105220185A, patent CN105274490A,
Patent CN103030104A etc..Such as patent CN105220185A proposes a kind of preparation side of super-amphiphobic micro-pillar array Surface Texture
7 steps such as method, including photoetching, electroforming, secondary electroforming, obtained regular mini column array structure is after carrying out low-surface-energy modification
Has good ultra-amphosphobic energy.Although this kind of thinking can realize excellent ultra-amphosphobic energy, is needed mostly using photoetching, done
The methods of method etching carries out many more manipulations, and technical difficulty is big, preparation efficiency is low and manufacturing cost is high, it is difficult to which batch prepares and in reality
Large-scale application during border is lived and produced.Second of mentality of designing is to grow to have in flat substrate or shallower micrometer structure substrate
The nanostructure of re-entrant angle feature, including nano thread structure, nanofibrous structures, nanorod structure, nanometer chip architecture, mesh nanometer
Structure and other nano-porous structures, as patent CN104372527A, patent CN102677141A, patent CN105820605A,
Patent CN107237128A and patent CN101545106 etc..Patent CN101545106 proposes that an a kind of step infusion method prepares metal
Metallic substrates are impregnated in perfluorinated aliphatic acid solution and obtain a nanometer chip architecture by the method for super-double-hydrophobic surface, coordinate perfluorinated aliphatic
The low free energy of hydrochlorate, realizes good ultra-amphosphobic.This kind of thinking generally use chemical method grows nanostructure, prepares
Journey is relatively easy, but the nanostructure grown is random growth, and only part nanostructure has re-entrant angle feature, therefore institute
The reentrant features of generation are often not abundant enough, cause its ultra-amphosphobic that can be weaker than the micrometer structure with re-entrant angle feature.In addition,
In practical application, super-double-hydrophobic surface will inevitably be stimulated by many external environments, such as mechanical damage, ultraviolet light spoke
According to, chemical reaction, germ contamination etc..Under the action of these external environments stimulate, the structure of conventional super-double-hydrophobic surface or at
Branch is damaged, and no longer has self-cleaning function, to lose application value.Therefore, the super double of high-durability how to be prepared
Hydrophobic surface is that current super-amphiphobic research field urgent problem to be solved and super-double-hydrophobic surface move towards practical application from laboratory
One big bottleneck.However, the super-double-hydrophobic surface reported does not well solve durability this problem also at present.
In conclusion it is simple, convenient, efficiently prepare and be still with excellent ultra-amphosphobic energy and the good surface of durability
One important topic.
Invention content
The object of the present invention is to provide a kind of super-amphiphobic metal surface of nanostructure distributed in three dimensions and its simply, efficiently
Preparation method utilizes ultrafast laser ablation to prepare and receive and pay out in micrometre array body structure surface with the complex method of chemical bath oxidation
The hierarchical structure of rice structure three-dimensional distribution so that a large amount of re-entrant angle nanostructure occurs in three dimensional micron body structure surface, and can be to micro-
Rice structure, nanostructure realize accuracy controlling respectively, to significantly improve the ultra-amphosphobic energy and durability of metal surface.
In order to achieve this, technical scheme is as follows：
A kind of super-amphiphobic metal surface of nanostructure distributed in three dimensions, the super-amphiphobic metal surface is on metal base
Three dimensional micron array structure is distributed with, nanostructure is distributed on its surface, the nanostructure is received by flexible, slim
The nanometer grass-like structure that rice silk fabric striped cell is wound mutually.
The width of silk ribbon shape structural unit of the present invention is 40~80nm, and the thickness of the silk ribbon shape structural unit is 1
~10nm.
Three dimensional micron array structure of the present invention is micron taper square array, and the height of the micron cone is 30~80
μm；Spacing between micron cone is 30~100 μm.
The ingredient of the three dimensional micron cone array structure is metal, and the ingredient of the nanometer grass-like structure is corresponding metal
Oxide.
A kind of preparation method of the metal super-double-hydrophobic surface of nanostructure distributed in three dimensions provided by the invention, it is characterised in that
This method comprises the following steps：
1) metal base pre-processes：After metal base is carried out grind away, polishing, ultrasound is carried out in ethyl alcohol, acetone successively
Cleaning, processing is dried after taking-up using stream of nitrogen gas；
2) preparation of metallic substrate surface three dimensional micron array structure：Using high power ultrafast laser in metallic substrate surface
Patterning ablation is carried out, three dimensional micron array structure is formed, is then cleaned by ultrasonic sample in ethyl alcohol, acetone successively,
Processing is dried using stream of nitrogen gas after taking-up；
3) preparation of three dimensional micron array structure nano surface grass-like structure：By the metal with three dimensional micron array structure
Base material carries out chemical bath processing in the oxidant configured, and metal base three dimensional micron array structure surface is made to grow nanometer
Grass-like structure forms the micro-nano two-stage structure of nanostructure distributed in three dimensions；
4) surface chemical modification of micro-nano two-stage structure：Metal surface with micro-nano two-stage structure is being configured
Fluorine-containing solution in carry out moditied processing, the time is 1~2 hour, and drying 1~2 is small at a temperature of 70~100 DEG C after taking-up
When to get to the super-amphiphobic metal surface of the nanostructure distributed in three dimensions.
In the step 2) of the method for the present invention, the patterning ablation is to be scanned according to square crossing form, adjacent
The spacing for scanning road is 30~100 μm, forms three dimensional micron and bores array structure, height is 30~80 μm.
In the step 3) of the method for the present invention, the oxidant is a concentration of 0.1~0.2mol/L ammonium persulfates and a concentration of 2
The mixed aqueous solution of the sodium hydroxide of~4mol/L；The temperature of the chemical bath processing is 25~100 DEG C, the chemical bath processing
Time be 20~40min.
In the step 4) of the method for the present invention, the fluorine-containing solution is the perfluoro decyl trimethoxy that mass fraction is 0.5~1%
The aqueous isopropanol of base silane.
Compared with prior art, the present invention has the following advantages and the technique effect of high-lighting：1. the present invention using laser,
Chemically composited method prepares micro nano structure super-double-hydrophobic surface, and micrometer structure, nanostructure can realize accurate tune respectively
Control.On micro-meter scale, by changing the parameter of high power ultrafast laser ablation process, such as laser power, scan path, scanning
The accuracy controlling of three dimensional micron planform, height, spacing etc. may be implemented in speed etc.；On nanoscale, by changeization
The parameter of oxidation process, such as the ingredient of oxidizing solution, each constituent concentration, oxidation treatment time are learned, nano junction may be implemented
It is configured the accuracy controlling of shape, size, density etc..2. the present invention is distributed in the technology of three-dimensional regular micrometer structure using nanostructure
Scheme may be implemented excellent ultra-amphosphobic energy, while have good durability.The present invention can be made by Optimal Parameters
Standby superelevation micrometer structure, and so that nano surface grass-like structure is in distributed in three dimensions (being distributed in three dimensional micron body structure surface)；One side
Face increases the growth area of nanostructure, on the other hand so that the nanostructure that original two dimension is grown up becomes three-dimensional lateral
Growth, to generate abundant local reentrant features, can realize excellent ultra-amphosphobic energy.Regular and depth is larger simultaneously
Micrometer structure can play a very good protection to the nanostructure on its surface, in face of mechanical wear or impact,
The better micrometer structure of mechanical strength bears extraneous destruction, the nano junction of dense distribution on the especially side wall of surface
Structure will not be destroyed obviously, and the function of super-amphiphobic can be still played so that super-double-hydrophobic surface is used for a long time without losing certainly
Cleaning function realizes good durability.3. the present invention compared with the prior art, have it is simple and practicable, rapidly and efficiently, can be big
A variety of clear superiorities such as area preparation.The present invention uses technical grade high power ultrafast laser, and peak power is up to 100W, simultaneously
It is aided with scanning galvanometer of the most high speed up to 11m/s, may be implemented efficiently to prepare, and prepares what area can be easily reached square metre
Magnitude.Meanwhile being aoxidized from laser ablation to chemical bath, whole process carries out under normal pressure, is very suitable for industrially carrying out big
Scale is efficiently prepared.4. the durability super-amphiphobic metal hierarchical structure surface energy of nanostructure distributed in three dimensions prepared by the present invention exists
It applies under a variety of external environments such as indoor and outdoor and keeps self-cleaning function, do not fail for a long time, in national defence, industrial production, day
Often the fields such as life are with a wide range of applications.
Description of the drawings
Fig. 1 is that the copper-based three-dimensional that the embodiment of the present invention 1 is prepared using femtosecond laser ablation, chemical bath oxidation complex method is micro-
The stereoscan photograph of the micro-nano two-stage structure of rice cone array and its nano surface grass.
Fig. 2 a, Fig. 2 b are that the embodiment of the present invention 1 aoxidizes the copper-based of complex method preparation using femtosecond laser ablation, chemical bath
The stereoscan photograph for the nanometer grass-like structure that three dimensional micron poppet surface is distributed in surface.
Fig. 3 a and Fig. 3 b are respectively the copper-based durability super-amphiphobic of nanostructure distributed in three dimensions prepared by the embodiment of the present invention 1
The contact angle of hierarchical structure surface and water and the contact angle with dodecane.
Fig. 4 is that the copper-based super-amphiphobic hierarchical structure surface of 1 gained nanostructure distributed in three dimensions of the embodiment of the present invention carries out
Stereoscan photograph after the solid particle impact test of 15min.
Fig. 5 a and Fig. 5 b are the copper-based super-amphiphobic hierarchical structure of 1 gained nanostructure distributed in three dimensions of the embodiment of the present invention respectively
Surface carry out after the solid particle impact test of 15min with the contact angle of water and with the contact angle of dodecane.
Fig. 6 a and Fig. 6 b are that the embodiment of the present invention 1 is prepared using femtosecond laser ablation, chemical bath oxidation complex method respectively
The stereoscan photograph of the stereoscan photograph and nanometer grass-like structure of micron cone array in aluminium base hierarchical structure surface.
Fig. 7 a and Fig. 7 b are the aluminium base durability super-amphiphobic of nanostructure distributed in three dimensions prepared by the embodiment of the present invention 1 respectively
The contact angle of hierarchical structure surface and water and the contact angle with dodecane.
Specific implementation mode
The present invention is described further with reference to the accompanying drawings and examples.
A kind of super-amphiphobic metal surface of nanostructure distributed in three dimensions provided by the invention, which is in metal
Three dimensional micron array structure is distributed on base material, nanostructure, the nanostructure is distributed in micrometre array body structure surface
In distributed in three dimensions, which is the nanometer being wound mutually by nanometer silk ribbon shape structural unit flexible and slim
Grass-like structure；The width of the silk ribbon shape structural unit may generally be 40~80nm, the thickness one of the silk ribbon shape structural unit
As can be 1~10nm.The micrometre array structure is preferably the square array of micron cone structure, and the height of the micron cone is
30~80 μm, the spacing between micron is bored is 30~100 μm.The ingredient of micron wimble structure is metal, affiliated nanometer grass-like structure
Ingredient be corresponding metal oxide, it is common such as copper oxide and aluminium oxide.
Fig. 1, Fig. 2 are that the present invention uses copper for base material, and first with femtosecond laser ablation, rule are prepared on Copper base material surface
Three dimensional micron wimble structure then recycles chemical bath oxidation complex method to prepare receiving for distributed in three dimensions on micron wimble structure surface
The stereoscan photograph of spartina shape structure.
The specific preparation method of the present invention includes the following steps：
1) metal base is pre-processed：After metal base is machined, polishing, successively in ethyl alcohol, acetone
It is cleaned by ultrasonic, processing then is dried using stream of nitrogen gas；
2) structure of metallic substrate surface rule micron cone array structure：Using high power ultrafast laser in metal base table
Face carries out selectivity patterning ablation, such as uses femtosecond laser, is scanned according to the pattern in square crossing road；Pattern is adjacent to be swept
The spacing for retouching path is 30~100 μm, and the pattern gross area is 0.01~10000mm2, to form the micron cone of high-sequential
Sample is then cleaned by ultrasonic in ethyl alcohol, acetone, place then is dried using stream of nitrogen gas by array structure successively
Reason；
3) the nanometer grass-like structure of micrometre array body structure surface is built：By the metal base with micrometre array structure with
Chemical bath processing is carried out in the oxidant set, to grow distributed in three dimensions on metal base three dimensional micron array structure surface
Nanometer grass-like structure, then carries out elution processing, and place is dried using stream of nitrogen gas using ethyl alcohol, acetone to sample successively
Reason, obtains micro-nano hierarchical structure；The oxidant can be water or a concentration of 0.1~0.2mol/L ammonium persulfates and concentration
For the mixed aqueous solution of the sodium hydroxide of 2~4mol/L；The temperature of the chemical bath processing is 25~100 DEG C, the chemical bath
The time of processing can be 20~40min.
4) to the metallic substrate surface chemical modification of micro-nano hierarchical structure：By the Metal Substrate with micro-nano hierarchical structure
Material carries out 1~2h of stewing process in the fluorine-containing solution configured, dries 1~2h after taking-up at a temperature of 70~100 DEG C, i.e.,
Obtain the super-amphiphobic metal surface of the nanostructure distributed in three dimensions.The fluorine-containing solution preferably use mass fraction for 0.5~
The aqueous isopropanol of 1% perfluoro decyl trimethoxy silane.
Several specific embodiments are enumerated below, to more fully understand the present invention.
Embodiment 1：The durable of nanostructure distributed in three dimensions is prepared using femtosecond laser ablation, chemical bath oxidation complex method
Property copper-based super-amphiphobic hierarchical structure surface：
1) by Copper base material be cut into size be 10mm × 10mm × 3mm copper billet, successively utilize No. 200, No. 400,800
Number, No. 1000, No. 1500 abrasive paper for metallograph polish Copper base material surface, be then processed by shot blasting.Then successively by copper billet
It is cleaned by ultrasonic in ethyl alcohol, acetone, processing then is dried using soft stream of nitrogen gas.
2) selectivity patterning ablation is carried out on Copper base material surface using High Power Femtosecond Laser, optical maser wavelength is
1030nm, pulse width 800fs, pulse recurrence frequency 200kHz, laser power 6W.Scan pattern is square crossing
Road, adjacent scan paths spacing are 40 μm, sweep speed 500mm/s, and scanning number of repetition is 40 times.By sample after laser ablation
Product are cleaned by ultrasonic in ethyl alcohol, acetone successively, and processing then is dried using soft stream of nitrogen gas.
3) configuration ammonium persulfate ((NH4)2S2O4) with the mixed aqueous solution of sodium hydroxide (NaOH) as oxidant, wherein
A concentration of 0.13mol/L of ammonium persulfate, a concentration of 2.5mol/L of sodium hydroxide；By copper billet sample obtained in the previous step 25
At DEG C in oxidant stewing process 20min, elution processing is carried out to sample, and is used using ethyl alcohol, acetone successively after taking-up
Processing is dried in soft stream of nitrogen gas.
4) configuration solute is perfluoro decyl trimethoxy silane, and solvent is the fluorization agent of isopropanol, wherein perfluoro decyl three
The mass fraction of methoxy silane is 0.5%.By copper billet sample stewing process 2h in fluorization agent obtained in the previous step, after taking-up
The drying and processing 2h in 80 DEG C of oven.The stereoscan photograph of micron cone array is as shown in Figure 1 in gained hierarchical structure.Micron
The stereoscan photograph of the nanometer grass-like structure of poppet surface distributed in three dimensions is as shown in Figure 2 a and 2 b.
The copper-based durability super-amphiphobic hierarchical structure surface of nanostructure distributed in three dimensions and the contact angle of water are up to 162 ° of (figures
3a), there is excellent ultra-amphosphobic energy up to 152 ° (Fig. 3 b) with the contact angle of dodecane.
The copper-based super-amphiphobic hierarchical structure surface of gained nanostructure distributed in three dimensions has good durability.Gained is received
After the copper-based super-amphiphobic hierarchical structure surface of rice structure three-dimensional distribution carries out the solid particle impact test of 15min, scanning electricity
For mirror photo as shown in figure 4, the contact angle with water is 158 ° (Fig. 5 a), the contact angle with dodecane is 144 ° (Fig. 5 b).
Embodiment 2 prepares the durable of nanostructure distributed in three dimensions using femtosecond laser ablation, chemical bath oxidation complex method
Property aluminium base super-amphiphobic hierarchical structure surface
1) by aluminium base be cut into size be 10mm × 10mm × 3mm aluminium block, successively utilize No. 200, No. 400,800
Number, No. 1000, No. 1500 abrasive paper for metallograph polish aluminium base surface, be then processed by shot blasting.Then successively by aluminium block
It is cleaned by ultrasonic in ethyl alcohol, acetone, processing is dried using soft stream of nitrogen gas after taking-up.
2) selectivity patterning ablation is carried out on aluminium base surface using High Power Femtosecond Laser, optical maser wavelength is
1030nm, pulse width 800fs, pulse recurrence frequency 200kHz, laser power 4W.Scan pattern is square crossing
Road, adjacent scan paths spacing are 40 μm, sweep speed 800mm/s, and scanning number of repetition is 30 times.By sample after laser ablation
Product are cleaned by ultrasonic in ethyl alcohol, acetone successively, and processing is dried using soft stream of nitrogen gas after taking-up.
3) aluminium block sample obtained in the previous step is handled into 20min at 100 DEG C in water, after taking-up successively utilize ethyl alcohol,
Acetone carries out elution processing to sample, and processing is dried using soft stream of nitrogen gas.
4) configuration solute is perfluoro decyl trimethoxy silane, and solvent is the fluorization agent of isopropanol, wherein perfluoro decyl three
The mass fraction of methoxy silane is 0.5%.By aluminium block sample stewing process 2h in fluorization agent obtained in the previous step, after taking-up
The drying and processing 2h in 80 DEG C of oven.The stereoscan photograph of micron cone array is as shown in Figure 6 a in gained hierarchical structure, micro-
The stereoscan photograph (as shown in Figure 6 b) of the nanometer grass-like structure of rice poppet surface distributed in three dimensions.
The aluminium base durability super-amphiphobic hierarchical structure surface of nanostructure distributed in three dimensions and the contact angle of water are up to 160 ° of (figures
7a), there is excellent ultra-amphosphobic energy up to 151 ° (Fig. 7 b) with the contact angle of dodecane.
Claims (9)
1. a kind of super-amphiphobic metal surface of nanostructure distributed in three dimensions, the super-amphiphobic metal surface are to divide on metal base
It is furnished with three dimensional micron array structure, nanostructure is distributed on its surface, the nanostructure is by flexible, slim nanometer
The nanometer grass-like structure that silk fabric striped cell is wound mutually.
2. a kind of super-amphiphobic metal surface of nanostructure distributed in three dimensions as described in claim 1, it is characterised in that：The silk fabric
The width of striped cell is 40~80nm, and thickness is 1~10nm.
3. a kind of super-amphiphobic metal surface of nanostructure distributed in three dimensions as claimed in claim 1 or 2, which is characterized in that institute
It is micron taper square array to state three dimensional micron array structure, and the height of the micron cone is 30~80 μm, between micron cone
Spacing is 30~100 μm.
4. a kind of metal super-double-hydrophobic surface of nanostructure distributed in three dimensions according to claim 3, it is characterised in that：It is described
The ingredient of three dimensional micron array structure is metal, and the ingredient of the nanometer grass-like structure is the oxide of corresponding metal.
5. a kind of preparation method of the super-amphiphobic metal surface of nanostructure distributed in three dimensions as described in claim 1, feature
It is that this method comprises the following steps：
1) metal base pre-processes：After metal base is machined, polishing, ultrasound is carried out in ethyl alcohol, acetone successively
Cleaning, reuses stream of nitrogen gas and processing is dried；
2) preparation of metallic substrate surface three dimensional micron array structure：It is carried out in metallic substrate surface using high power ultrafast laser
Ablation is patterned, three dimensional micron array structure is formed, is then cleaned by ultrasonic sample in ethyl alcohol, acetone successively, then make
Processing is dried with stream of nitrogen gas；
3) preparation of three dimensional micron array structure nano surface grass-like structure：By the metal base with three dimensional micron array structure
Chemical bath processing is carried out in the oxidant configured, and metal base three dimensional micron array structure surface is made to grow a nanometer grass-like
Structure forms the micro-nano two-stage structure of nanostructure distributed in three dimensions；
4) surface chemical modification of micro-nano two-stage structure：Metal surface with micro-nano two-stage structure is contained what is configured
Carry out moditied processing in fluorine solution, the time is 1~2 hour, then dried at a temperature of 70~100 DEG C 1~2 hour to get
To the super-amphiphobic metal surface of the nanostructure distributed in three dimensions.
6. a kind of preparation method of the super-amphiphobic metal surface of nanostructure distributed in three dimensions according to claim 5, special
Sign is：Patterning ablation described in step 2) is to be scanned according to square crossing form, and the spacing in adjacent scanning road is
It 30~100 μm, forms three dimensional micron and bores array structure, height is 30~80 μm.
7. a kind of preparation method of the super-amphiphobic metal surface of nanostructure distributed in three dimensions according to claim 5, special
Sign is：Oxidant described in step 3) is the hydrogen-oxygen of a concentration of 0.1~0.2mol/L ammonium persulfates and a concentration of 2~4mol/L
Change the mixed aqueous solution of sodium.
8. a kind of preparation method of the super-amphiphobic metal surface of nanostructure distributed in three dimensions according to claim 5, special
Sign is：The temperature of the processing of chemical bath described in step 3) is 25~100 DEG C, time of chemical bath processing is 20~
40min。
9. a kind of preparation method of the metal super-double-hydrophobic surface of nanostructure distributed in three dimensions according to claim 5, special
Sign is：Fluorine-containing solution described in step 4) is the isopropanol for the perfluoro decyl trimethoxy silane that mass fraction is 0.5~1%
Solution.
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| CN201810316726.4A CN108466015B (en) | 2018-04-10 | 2018-04-10 | Super-amphiphobic metal surface with three-dimensional distribution of nano structure and preparation method thereof |
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| CN201810316726.4A CN108466015B (en) | 2018-04-10 | 2018-04-10 | Super-amphiphobic metal surface with three-dimensional distribution of nano structure and preparation method thereof |
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| CN108466015B CN108466015B (en) | 2020-09-29 |
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| CN201810316726.4A Active CN108466015B (en) | 2018-04-10 | 2018-04-10 | Super-amphiphobic metal surface with three-dimensional distribution of nano structure and preparation method thereof |
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| CN109534286A (en) * | 2018-11-05 | 2019-03-29 | 广州大学 | A kind of material surface nesting nanostructure and preparation method thereof |
| CN109881193A (en) * | 2019-04-25 | 2019-06-14 | 清华大学 | A kind of stable ultra-hydrophobic metal surface of three-dimensional three-level micro-nano structure and preparation method |
| CN109974512A (en) * | 2019-03-21 | 2019-07-05 | 中国科学院理化技术研究所 | A kind of micro-nano complex intensifying boiling structure of material surface and its preparation method and application |
| CN110116273A (en) * | 2019-06-05 | 2019-08-13 | 北京理工大学 | The method that femtosecond laser synergistic oxidation reaction prepares broad band anti-reflection structure |
| CN112222766A (en) * | 2020-09-14 | 2021-01-15 | 西南科技大学 | Orientation surface preparation method for controlling directional bounce of liquid drop |
| CN114094115A (en) * | 2021-10-13 | 2022-02-25 | 中国长江三峡集团有限公司 | Columnar copper array current collector and preparation method and application thereof |
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