CN100463858C - Ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film and preparing method thereof - Google Patents
Ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film and preparing method thereof Download PDFInfo
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- CN100463858C CN100463858C CNB2006100116431A CN200610011643A CN100463858C CN 100463858 C CN100463858 C CN 100463858C CN B2006100116431 A CNB2006100116431 A CN B2006100116431A CN 200610011643 A CN200610011643 A CN 200610011643A CN 100463858 C CN100463858 C CN 100463858C
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Abstract
The present invention relates to a superhydrophobic laminarization composite metal oxides film with two hydroxide radicals which grows in the aluminium matrix and the preparation method of the same; wherein the surface of the aluminium matrix is subjected to anodic oxidation; the laminarization composite metal oxides film of the present invention has a micromillimeter/micron composite structure, has scraggly fluctuatings of micron level on the surface, has excellent hydrophobicity after being subjected to hydrophobic treatment on the surface in the solution of long chain fatty acid salt surface active agent, and has a contact angle of 150~170 degrees with water drop. The surface active agent solution used in the present invention is free of fluorin, has no toxic action to human body and no pollution to environment. The method of the present invention has a simple process, available raw materials, low cost, and excellent repeatability. The obtained film of the present invention has excellent hydrophobicity and self-cleaning property, and can be used as the dust prevention and fog prevention overcoating on the surface of the metal of engineering material.
Description
Technical field:
The invention belongs to the thin-film material technical field, be specifically related to a kind of ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film on the surperficial anodised aluminum substrate and preparation method thereof that is grown in.
Technical background:
Layered di-hydroxyl composite metal oxidate (claim houghite again, be called for short LDHs) is an anionoid type laminate structure functional materials, and by being parallel to each other and positively charged laminate is formed, interlayer is made of balance anion and water molecules.Its chemical constitution general formula is: [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N- X/n) mH
2O, wherein M
2+, M
3+Be respectively divalence, the trivalent metal ion that is positioned on the laminate, A
N-Represent interlayer anion.This class material is because its unique crystalline structure and physicochemical characteristic make it show very wide application prospect in many fields such as ion-exchange, absorption, catalysis, macromolecule modified, optical material, magnetics material, electricity materials.
In recent years, super hydrophobic surface has caused people's common concern.So-called super hydrophobic surface generally is meant and the contact angle of the water droplet surface greater than 150 °.It has been generally acknowledged that micron and nanophase bonded composite structure are the basic reasons that causes surface super hydrophobic, and produce super hydrophobic surface therefrom and have bigger contact angle.Super hydrophobic surface have simultaneously waterproof, anti-pollution, anti-oxidant, strengthen biocompatibility, oilness and prevent character such as conduction of current.At occurring in nature, super-hydrophobic phenomenon also is extensively to exist, and because of there is one deck super hydrophobic film in its surface, makes water droplet be easy to tumble on its surface as lotus leaf, mud foreign material on the lotus leaf surface etc. can also be taken away when water droplet tumbles; Equally also there are similar super-drainage structure in the wing of butterfly, the feather of birds.Super hydrophobic material all has extremely wide application prospect in industrial and agricultural production and daily life.For example: fields such as weaving, coating, gene transmission, microfluid and the conveying of free of losses liquid.
In general, super hydrophobic surface can prepare by two kinds of methods.A kind of is to make up coarse structure on hydrophobic material (contact angle is greater than 90 °) surface, is commonly considered as having under the situation of micron and nano composite structure, and roughness is high more good more.Another kind is with low surface energy material (as silicon fluoride, longer chain fatty acid) uneven surface to be modified.Bibliographical information all is that a kind of method prepares super hydrophobic surface before adopting mostly at present.For example: at document Angew.Chem.Int.Ed, 2003 (42): 1433 and Angew.Chem.Int.Ed, 2003 (43): in 4338, people such as Jiang Lei make up coarse structure on hydrophobic macromolecule material film surface makes film surface demonstrate excellent ultra-hydrophobicity.Other method such as gas ions polymerization or etching, microwave plasma strengthen chemical vapour deposition, anodic oxidation and template and also can belong to and be first method.In order effectively to obtain super hydrophobic surface, with the low surface energy material surface is modified also and be necessary.Mostly the current low surface energy material that adopts is fluorochemicals or organosilane.As document J.Am.Chem.Soc, 2005 (127): in 15670, people such as Liu adopt C
9F
20And PDMSVT (poly (dimethylsiloxane) vinyl terminated) modifies the super-hydrophobic engineering materials that has obtained stable performance to aluminium and aluminum alloy surface.The patent No. is in the CN99810647.X patent, and the applicant is coated in hydrofluoric ether and has obtained contact angle on the ground after the surface treatment greater than 120 ° hydrophobic film.
Because various fluorine cpd are on the rise to environment damage, each state of our times all bans use of this compounds, so the researchist just actively seeks the surrogate of fluorochemical, the research of super-hydrophobic boundary material is no exception.The layered di-hydroxyl composite metal oxidate film that we are prepared has the scraggly uneven surface of micron order, carries out having very superior hydrophobic performance after surface hydrophobicity handles in cheap hard soap surfactant soln.Employed long-chain carboxylic acid's tensio-active agent is not fluorine-containing, and human body is not had any toxic action and environmentally safe.
Summary of the invention:
The purpose of this invention is to provide a kind of ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film; Another purpose provides the preparation method of this ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film.
Ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film provided by the invention is to be grown in the LDHs film of surface on the aluminium substrate after the anodic oxidation, and the chemical general formula of rete LDHs is:
[M
2+ 1-xAl
3+ x(OH)
2]
x+(Y
m-)
x/m·yH
2O，
M wherein
2+Represent divalent-metal ion Mg
2+, Co
2+, Ni
2+, Ca
2+, Cu
2+, Fe
2+, Mn
2+In any, that preferable is Ni
2+, Co
2+Or Mg
2+0.2≤x≤0.4,0≤y≤2; M is the valence mumber of Y, Y
M-Represent interlayer anion CO
3 2-, NO
3 -, SO
4 2-, Cl
-, F
-Or Br
-
This LDHs film has the Nano/micron composite structure, and there is the scraggly fluctuating of micron order in the surface; This LDHs film has ultra-hydrophobicity through the processing of water-soluble long-chain soap surfactant soln, and the contact angle of itself and water droplet is at 150～170 °;
Described water-soluble long-chain soap tensio-active agent, its chemical formula is C
N-1H
2n-1COO
-M
+, n=12～22 wherein; M
+Represent monovalent metallic ion K
+, Na
+The better water solubility hard soap is C
11H
21COONa, C
11H
21COOK, C
16H
31COONa, C
16H
31COOK, C
18H
35COONa or C
18H
35One of COOK is more preferably C
11H
21COONa or C
11H
21COOK.
The present invention adopts the original position synthetic technology, on the aluminium flake after the anodic oxidation, make the layered di-hydroxyl composite metal oxidate film on the surface, this LDHs film has the Nano/micron composite structure, and there is the scraggly fluctuating of micron order in the surface, adopt the hard soap surfactant soln that film surface is carried out hydrophobic treatment again, film surface after the hydrophobic treatment has still kept this Nano/micron composite structure, between the Nano/micron composite structure surface layer and the globule, form one deck air film, with the contact angle of water droplet up to 170 °, sewage splashes the surface and can tumble automatically, do not stay any vestige, can reach from clean purpose.
Concrete preparation method is as follows:
A. with purity greater than 80%, thickness is used ethanol ultrasonic cleaning 5～10min earlier at the aluminium flake of 0.01～1mm, water ultrasonic cleaning 5～10min removes surface and oil contaminant again, make anode then on anodic oxidation device, make negative electrode with stereotype or stainless steel plate, electrolytic solution is the sulphuric acid soln of 0.5～3.0mol/L, oxidation current is 1～5A, with taking out behind aluminium flake anodic oxidation 30～100min, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film;
B. with ammonium nitrate and solubility divalence inorganic salt M
2+Y
M- 2/mMol ratio by 3～30 is dissolved in the deionized water, M
2+Concentration of metal ions is controlled at 0.01～0.5mol/L, and the pH value of the weak ammonia conditioned reaction solution with 1% is 4.5～10, obtains reaction soln;
C. the anodised aluminium substrate in surface is suspended in the reaction soln, reacted 0.5～96 hour down, take out aluminium substrate at 25～180 ℃, at room temperature dry after the ethanolic soln rinsing, promptly obtain layered di-hydroxyl composite metal oxidate (LDHs) film;
D. with layered di-hydroxyl composite metal oxidate (LDHs) membrane suspended for preparing in the surfactant soln of 0.001～0.5mol/L, reacted 0.5～20 hour down at 25～100 ℃, hard soap combines with the hydrotalcite surface hydroxyl and forms covalent linkage, use the ethanol rinsing after taking out film, at room temperature dry, promptly obtain having layered di-hydroxyl composite metal oxidate (LDHs) film of ultra-hydrophobicity.
M among the step B
2+Be Mg
2+, Co
2+, Ni
2+, Ca
2+, Cu
2+, Fe
2+, Mn
2+In any, that preferable is Ni
2+, Co
2+Or Mg
2+, Y
M-Be CO
3 2-, NO
3 -, SO
4 2-, Cl
-, F
-, Br
-In any, that preferable is CO
3 2-, NO
3 -Or Cl
-The preferable pH value scope of reaction soln is 5.5～8.5.
The preferable reaction conditions of step C is to react 3～60 hours down at 50～150 ℃, and better reaction conditions is 50～130 ℃ of reactions down, 5～20 hours.
The described surfactant soln of step D is the water-soluble long-chain soap that satisfies following condition, and its chemical formula is C
N-1H
2n-1COO
-M
+, n=12～22 wherein; M
+Represent monovalent metallic ion K
+, Na
+Preferably lauric acid sodium salt or sylvite (C
11H
21COONa or C
11H
21COOK), Palmiticacid sodium salt or sylvite (C
16H
31COONa or C
16H
31COOK), stearic acid sodium salt or sylvite (C
18H
35COONa or C
18H
35COOK)); Best is lauric acid sodium salt or sylvite.
The preferable reaction conditions of step D is to react 0.5～10 hour down at 25～80 ℃, and better reaction conditions is to react 2～5 hours down at 30～50 ℃.
Adopt Japanese HITACHI S-3500N type scanning electronic microscope (SEM) observation based superhydrophobic thin films surface topography (for more clear all the SEM samples of photograph are all handled through metal spraying).Fig. 1 is the SEM photograph on the aluminium flake surface after the surface anodic oxidation of embodiment 1 steps A gained, and Fig. 2 is the surperficial SEM photograph of the LDHs film sample of embodiment 1 step C preparation.Can be clear that by Fig. 2, on the anodised aluminium surface, there is one deck sexangle sheet material, i.e. LDHs thin film layer of Xing Chenging, hydrotalcite sexangle sheet crystal grain vertical-growth is at matrix surface, hexagonal summit is the nano level range scale, and hexagonal each bar limit yardstick is in the micron order scope, and this Nano/micron composite structure has caused film to have very high degree of roughness, and hexagonal disks and sheet are interlaced in the thin film layer, form the special appearance of nest like.The thickness of this LDHs layer is about 1.5 μ m microns.Fig. 3 is the SEM photograph of the super-hydrophobic LDHs film sample of embodiment 1 step D preparation.Comparison diagram 2 and Fig. 3 can find that the pattern of the film after hydrophobization is handled does not change with preceding the comparing basically of processing, has still kept the nest like pattern.
Adopting the German KR ü SS GmbH DSA100 of company type to drip the conformal analysis system measures the contact angle of super-hydrophobic LDHs film of gained and water droplet.The back average after the same film sample surface measurement five times as last contact angle observed value.Fig. 4 is the optical photograph of water droplet on the super-hydrophobic LDHs film sample surface of embodiment 1 preparation.Fig. 5 is the in kind photo of water droplet at the super-hydrophobic LDHs film sample of embodiment 1 step D preparation.
The invention has the beneficial effects as follows: prepared layered di-hydroxyl composite metal oxidate film has the Nano/micron composite structure, and there is the scraggly fluctuating of micron order in the surface, after in the hard soap surfactant soln, carrying out the surface hydrophobicity processing, have very superior hydrophobic performance, with the contact angle of water droplet up to 170 °.Employed surfactant soln is not fluorine-containing, and human body is not had any toxic action and environmentally safe.The used technology of this law is simple, raw material is easy to get, cost is low, good reproducibility; the film that makes has good super-hydrophobic and self-cleaning property, and this super-hydrophobicity layered di-hydroxyl composite metal oxidate film is expected to use as dustproof, the antifog supercoat of metallic surface in the engineering materials.
Description of drawings
Fig. 1 is the SEM photograph on the aluminium flake surface after the surperficial anodic oxidation of embodiment 1 steps A gained;
Fig. 2 is the surperficial SEM photograph of the LDHs film sample that obtains of embodiment 1 step C;
Fig. 3 is the SEM photograph of the super-hydrophobic LDHs film sample that obtains of embodiment 1 step D.
Fig. 4 is the optical photograph of water droplet on the super-hydrophobic LDHs film sample surface of embodiment 1 preparation.
Fig. 5 is the in kind photo of water droplet at the super-hydrophobic LDHs film sample of embodiment 1 preparation.
Embodiment:
The invention will be further described below in conjunction with embodiment:
Embodiment 1:
A. the aluminium flake that with thickness is 0.1mm (purity is 99.5%) is earlier with ethanol ultrasonic cleaning 5min, water ultrasonic cleaning 5min removes surface and oil contaminant again, and anodic oxidation 50min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is the sulphuric acid soln of 1.0mol/L, and oxidation current is 2A.
B. in the 1L Erlenmeyer flask, with 1mol Ni (NO
3)
26H
2O and 6mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 7.5 again.
C. the anodised aluminium substrate in surface is suspended in the solution, behind the sealed vessel, isothermal reaction is 36 hours under 45 ℃ of temperature, and question response finishes the back and takes out aluminium substrate, rinses well with deionized water, uses the ethanol rinsing again, at room temperature dries, and promptly obtains the LDHs film.
D. with above-mentioned LDHs membrane suspended in 0.05mol/L sodium laurate (C
11H
21COONa) carried out the individual layer self-assembling reaction 5 hours under 25 ℃ in the aqueous solution, use the ethanol rinsing behind the taking-up film, at room temperature drying obtains super-hydrophobic LDHs film.
The SEM photograph on the aluminium flake surface after the gained surface anodic oxidation is seen Fig. 1, and the SEM photo of LDHs film is seen Fig. 2.The SEM photograph of super-hydrophobic LDHs film sample is seen Fig. 3.Water droplet is seen Fig. 4 at the optical photograph on super-hydrophobic LDHs film sample surface.Water droplet is seen Fig. 5 in the pictorial diagram of film surface.Recording water droplet is 165 ± 3 ° at the contact angle of film surface.
Embodiment 2:
A. the aluminium flake that with thickness is 0.1mm (purity is 99.5%) is earlier with ethanol ultrasonic cleaning 5min, water ultrasonic cleaning 5min removes surface and oil contaminant again, and anodic oxidation 50min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is the sulphuric acid soln of 1.0mol/L, and oxidation current is 2A.
B. in the 1L Erlenmeyer flask, with 2mol Ni (NO
3)
26H
2O and 12mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 8.5 again.
C. the anodised aluminium substrate in surface is suspended in the solution, behind the sealed vessel, isothermal reaction is 24 hours under 75 ℃ of temperature, and question response finishes the back and takes out aluminium substrate, rinses well with deionized water, uses the ethanol rinsing again, at room temperature dries, and promptly obtains the LDHs film.
D. with above-mentioned LDHs membrane suspended in 0.005mol/L sodium stearate (C
18H
35COONa) carried out the individual layer self-assembling reaction 10 hours under 80 ℃ in the aqueous solution, use the ethanol rinsing behind the taking-up film, at room temperature drying obtains super-hydrophobic LDHs film.Recording water droplet is 153 ± 3 ° at the contact angle of film surface.
Embodiment 3:
A. the aluminium flake that with thickness is 0.1mm (purity is 99.5%) is earlier with ethanol ultrasonic cleaning 5min, water ultrasonic cleaning 5min removes surface and oil contaminant again, and anodic oxidation 50min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is the sulphuric acid soln of 1.0mol/L, and oxidation current is 2A.
B. in the 1L Erlenmeyer flask, with 0.5Co (NO
3)
26H
2O and 6mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 6.5 again.
C. the anodised aluminium substrate in surface is suspended in the solution, behind the sealed vessel, isothermal reaction is 21 hours under 45 ℃ of temperature, and question response finishes the back and takes out aluminium substrate, rinses well with deionized water, uses the ethanol rinsing again, at room temperature dries, and promptly obtains the LDHs film.
D. with above-mentioned LDHs membrane suspended in 0.025mol/L potassium laurate (C
11H
21COOK) carried out the individual layer self-assembling reaction 5 hours under 40 ℃ in the aqueous solution, use the ethanol rinsing behind the taking-up film, at room temperature drying obtains super-hydrophobic LDHs film.Water droplet is 167 ± 3 ° at the contact angle of film surface.
Embodiment 4:
A. the aluminium flake that with thickness is 0.5mm (purity is 80%) is earlier with ethanol ultrasonic cleaning 10min, water ultrasonic cleaning 5min removes surface and oil contaminant again, and anodic oxidation 100min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is the sulphuric acid soln of 2.0mol/L, and oxidation current is 2A.
B. in the 1L Erlenmeyer flask, with 1mol Co (NO
3)
26H
2O and 12mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 6.8 again.
C. the anodised aluminium substrate in surface is suspended in the solution, behind the sealed vessel, isothermal reaction is 28 hours under 90 ℃ of temperature, and question response finishes the back and takes out aluminium substrate, rinses well with deionized water, uses the ethanol rinsing again, at room temperature dries, and promptly obtains the LDHs film.
D. with above-mentioned LDHs membrane suspended in 0.0025mol/L potassium stearate (C
18H
35COOK) carried out self-assembling reaction 2 hours under 70 ℃ in the aqueous solution, use the ethanol rinsing behind the taking-up film, at room temperature drying obtains super-hydrophobic LDHs film.Recording water droplet is 154 ± 3 ° at the contact angle of film surface.
Embodiment 5:
A. the aluminium flake that with thickness is 0.5mm (purity is 80%) is earlier with ethanol ultrasonic cleaning 10min, water ultrasonic cleaning 5min removes surface and oil contaminant again, and anodic oxidation 100min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is the sulphuric acid soln of 1.5mol/L, and oxidation current is 2A.
B. in the 1L Erlenmeyer flask, with 0.8mol Co (NO
3)
26H
2O and 5mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 5.0 again.
C. the anodised aluminium substrate in surface is suspended in the solution, behind the sealed vessel, isothermal reaction is 16 hours under 60 ℃ of temperature, and question response finishes the back and takes out aluminium substrate, rinses well with deionized water, uses the ethanol rinsing again, at room temperature dries, and promptly obtains the LDHs film.
D. with above-mentioned LDHs membrane suspended in 0.02mol/L sodium palmitate (C
16H
31COONa) carried out self-assembling reaction 8 hours in 45 ℃ of following aqueous solution, the ethanol rinsing is used in the back, and at room temperature drying obtains super-hydrophobic LDHs film.Recording water droplet is 158 ° ± 3 ° at the contact angle of film surface.
Embodiment 6:
A. the aluminium flake that with thickness is 0.5mm (purity is 80%) is earlier with ethanol ultrasonic cleaning 10min, water ultrasonic cleaning 5min removes surface and oil contaminant again, and anodic oxidation 100min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is the sulphuric acid soln of 1.5mol/L, and oxidation current is 2A.
B. in the 1L Erlenmeyer flask, with 1mol Co (NO
3)
26H
2O and 6mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 8.2 again.
C. the anodised aluminium substrate in surface is suspended in the solution, behind the sealed vessel, isothermal reaction is 17 hours under 80 ℃ of temperature, and question response finishes the back and takes out aluminium substrate, rinses well with deionized water, uses the ethanol rinsing again, at room temperature dries, and promptly obtains the LDHs film.
D. with above-mentioned LDHs membrane suspended in 0.1mol/L Palmiticacid potassium (C
16H
31COOK) carried out self-assembling reaction 5 hours under 60 ℃ in the aqueous solution, the ethanol rinsing is used in the back, and at room temperature drying obtains super-hydrophobic LDHs film.Water droplet is 151 ° ± 2 ° at the contact angle of film surface.
Claims (8)
1. a ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film is to be grown in the LDHs film of surface on the aluminium flake after the anodic oxidation, and wherein the LDHs film is meant layered di-hydroxyl composite metal oxidate, and the chemical general formula of rete LDHs is:
[M
2+ 1-xAl
3+ x(OH)
2]
x+(Y
m-)
x/m·yH
2O，
M wherein
2+Represent divalent-metal ion Mg
2+, Co
2+, Ni
2+, Ca
2+, Cu
2+, Fe
2+, Mn
2+In any; M is the valence mumber of Y, Y
M-Represent interlayer anion CO
3 2-, NO
3 -, SO
4 2-, Cl
-, F
-Or Br
-0.2≤x≤0.4,0≤y≤2;
This LDHs film has nanometer and micron composite structure, and there is the scraggly fluctuating of micron order in the surface; This LDHs film has ultra-hydrophobicity through the processing of water-soluble long-chain soap surfactant soln, and the contact angle of itself and water droplet is at 150～170 °;
Described water-soluble long-chain soap tensio-active agent, its chemical formula is C
N-1H
2n-1COO
-M
+, n=12～22 wherein; M
+Represent monovalent metallic ion K
+Or Na
+
2. a ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film as claimed in claim 1 is characterized in that, described LDHs film has passed through C
11H
21COONa, C
11H
21COOK, C
16H
31COONa, C
16H
31COOK, C
18H
35COONa or C
18H
35The processing of the water-soluble long-chain soap of one of COOK; Described M
2+Be Ni
2+, Co
2+Or Mg
2+Y
M-Be CO
3 2-, NO
3 -Or Cl
-
3. a ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film as claimed in claim 1 is characterized in that this LDHs film has passed through C
11H
21COONa or C
11H
21The processing of COOK.
4. the preparation method of a ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film as claimed in claim 1, concrete steps are as follows:
A. with purity greater than 80%, thickness is used ethanol ultrasonic cleaning 5～10min earlier at the aluminium flake of 0.01～1mm, water ultrasonic cleaning 5～10min removes surface and oil contaminant again, make anode then on anodic oxidation device, make negative electrode with stereotype or stainless steel plate, electrolytic solution is the sulphuric acid soln of 0.5～3.0mol/L, oxidation current is 1～5A, with taking out behind aluminium flake anodic oxidation 30～100min, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film;
B. with ammonium nitrate and solubility divalence inorganic salt M
2+Y
M- 2/mMol ratio by 3～30 is dissolved in the deionized water, M
2+Concentration of metal ions is controlled at 0.01～0.5mol/L, and the pH value of the weak ammonia conditioned reaction solution with 1% is 4.5～10, obtains reaction soln;
Solubility divalence inorganic salt M
2+Y
M- 2/mMiddle M
2+Be Mg
2+, Co
2+, Ni
2+, Ca
2+, Cu
2+, Fe
2+, Mn
2+In any one, Y
M-Be CO
3 2-, NO
3 -, SO
4 2-, Cl
-, F
-, Br
-In any one;
C. the anodised aluminium flake in surface is suspended in the reaction soln, reacted 0.5～96 hour down, take out aluminium flake at 25～180 ℃, at room temperature dry after the ethanolic soln rinsing, promptly obtain the layered di-hydroxyl composite metal oxidate film;
D. with the layered di-hydroxyl composite metal oxidate membrane suspended for preparing in the water-soluble long-chain soap surfactant soln of 0.001～0.5mol/L, reacted 0.5～20 hour down at 25～100 ℃, hard soap combines with the layered di-hydroxyl composite metal oxidate surface hydroxyl and forms covalent linkage, use the ethanol rinsing after taking out film, at room temperature dry, promptly obtain having the layered di-hydroxyl composite metal oxidate film of ultra-hydrophobicity;
The described water-soluble long-chain soap of step D, its chemical formula is C
N-1H
2n-1COO
-M
+, n=12～22 wherein; M
+Represent monovalent metallic ion K
+Or Na
+
5. the preparation method of ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film according to claim 4 is characterized in that: M among the step B
2+Be Ni
2+, Co
2+Or Mg
2+Y
M-Be CO
3 2-, NO
3 -Or Cl
-The pH value scope of reaction soln is 5.5～8.5;
The reaction conditions of step C is to react 3～60 hours down at 50～150 ℃;
The described water-soluble long-chain soap of step D is lauric acid sodium salt, lauric acid sylvite, Palmiticacid sodium salt, Palmiticacid sylvite, stearic acid sodium salt or stearic acid sylvite.
6. the preparation method of ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film according to claim 4 is characterized in that: the reaction conditions of step C is 50～130 ℃ of reactions down, 5～20 hours;
The described water-soluble long-chain soap of step D is lauric acid sodium salt or sylvite.
7. the preparation method of ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film according to claim 4, the reaction conditions that it is characterized in that step D is 25～80 ℃ of reactions 0.5～10 hour down.
8. the preparation method of ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film according to claim 4, the reaction conditions that it is characterized in that step D is 30～50 ℃ of reactions 2～5 hours down.
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Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008151495A1 (en) * | 2007-06-15 | 2008-12-18 | Beijing University Of Chemical Technology | Super-hydrophobic double-layered-hydroxides thin film and the method for making the same |
| CN101748461B (en) * | 2008-12-02 | 2011-10-19 | 中国科学院兰州化学物理研究所 | Super-hydrophobic and super-oleophobic surface preparation technology |
| CN101985250B (en) * | 2009-07-29 | 2013-08-28 | 财团法人工业技术研究院 | Weather-resistant self-cleaning coating and forming method thereof |
| CN102345149B (en) * | 2011-09-16 | 2014-05-14 | 东南大学 | Preparation method of aluminium foil bionic nanostructured super-hydrophobic anti-condensation functional surface |
| CN102976278B (en) * | 2012-12-19 | 2014-03-19 | 青岛科技大学 | Laminar bimetal hydroxide and preparation method thereof |
| CN103938431B (en) * | 2014-04-19 | 2016-01-27 | 青岛农业大学 | The super-hydrophobic cloth adopting layered double-hydroxide to prepare and preparation technology thereof |
| CN104032297A (en) * | 2014-06-03 | 2014-09-10 | 南车青岛四方机车车辆股份有限公司 | Film forming liquid of aluminum alloy surface conversion film as well as preparation method and application thereof |
| CN107001061B (en) * | 2014-12-17 | 2019-05-17 | 日本碍子株式会社 | Layered double-hydroxide film and composite material containing layered double-hydroxide |
| CN104672967A (en) * | 2015-01-28 | 2015-06-03 | 西北师范大学 | Preparation method of colored superhydrophobic coating with outstanding corrosion resistance |
| CN105018999B (en) * | 2015-07-09 | 2017-07-28 | 哈尔滨工程大学 | The method of aluminum alloy differential arc oxidation film growth in situ layered double hydroxide |
| CN106400079A (en) * | 2016-11-16 | 2017-02-15 | 北京石油化工学院 | Preparation method of multiple super-hydrophobic composite film layers on aluminium alloy surface |
| CN107913723B (en) * | 2017-12-08 | 2020-06-23 | 山东理工大学 | Chromium-containing three-dimensional nickel-aluminum hydrotalcite-like film and preparation method and application thereof |
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| CN110130098B (en) * | 2019-05-14 | 2020-07-24 | 北京化工大学 | Super-hydrophobic hydrotalcite composite membrane and preparation method thereof |
| CN110724992B (en) * | 2019-09-27 | 2021-07-09 | 江苏科技大学 | Method for preparing corrosion-resistant super-hydrophobic film on surface of aluminum alloy |
| CN110767544A (en) * | 2019-10-31 | 2020-02-07 | 华南理工大学 | Thin film electrode and liquid phase self-climbing preparation method and application thereof |
| CN112095092A (en) * | 2020-08-13 | 2020-12-18 | 华南理工大学 | Method for preparing high-performance super-hydrophobic stainless steel by utilizing nano layered double hydroxide and prepared high-performance super-hydrophobic stainless steel |
| CN113046689B (en) * | 2021-03-05 | 2022-12-06 | 苏州鱼得水电气科技有限公司 | Super-hydrophobic corrosion-resistant aluminum alloy for biomedical treatment and preparation method thereof |
| CN113073322A (en) * | 2021-03-29 | 2021-07-06 | 中国科学院宁波材料技术与工程研究所 | Magnesium alloy surface corrosion-resistant super-hydrophobic film layer and preparation method and application thereof |
| CN113445051B (en) * | 2021-07-13 | 2022-04-01 | 中国石油大学(华东) | Method for preparing super-hydrophobic lithium-aluminum hydrotalcite-like coating on surface of aluminum alloy porous oxide film |
| CN114300270A (en) * | 2022-01-25 | 2022-04-08 | 天津大学 | Preparation method of multilayer ceramic capacitor structure with waterproof and breakdown-resistant characteristics |
| CN114988519A (en) * | 2022-06-24 | 2022-09-02 | 湘潭大学 | Oil-water separation membrane and preparation method and application thereof |
| CN117230656B (en) * | 2023-11-14 | 2024-02-02 | 青州金昊新材料有限公司 | Waterproof agent for paper pulp molding material and preparation method |
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