CN101113012A - Highly-adherent super-hydrophobic double-functional intercalation configuration type hydrotalcite film and method for preparing same - Google Patents

Highly-adherent super-hydrophobic double-functional intercalation configuration type hydrotalcite film and method for preparing same Download PDF

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CN101113012A
CN101113012A CNA2006100889938A CN200610088993A CN101113012A CN 101113012 A CN101113012 A CN 101113012A CN A2006100889938 A CNA2006100889938 A CN A2006100889938A CN 200610088993 A CN200610088993 A CN 200610088993A CN 101113012 A CN101113012 A CN 101113012A
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ldhs
film
deionized water
preparation
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CN100560501C (en
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张法智
付珊珊
段雪
陈虹芸
徐赛龙
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention relates to a high adhesive super-hydrophobic double function intercalated structure thin film material and the preparation method thereof. Under the protection of inert gas, layered double hydroxy metal complex oxide thin film in situ grows at the aluminium metal substrate that is anodic oxidized, then after ion exchange, surfactant anion of long chain fatty salt is inserted between the layers and the thin film has Nano/micron composite structure. The intercalated structure thin film prepared not only has excellent hydrophobic effect for the contact angle reaches to 172 degrees, but also has high adhesive function towards water, which results in that the water does not drip or falls down when the substrate is inclined or inverted. Due to the strong interaction between the hydrotalcite-like compounds laminate and interlayer surface active agent anion, the high adhesive and super-hydrophobic materials obtained has better thermal stability. The method has simple process, moderate synthesis conditions, easy operation and excellent binding force between the thin film prepared and the substrate. The super-hydrophobic thin film is hopeful to be applied as damage free liquid transportation material and liquid carrying material, biological micro solution pipette, etc.

Description

Highly-adherent super-hydrophobic double-functional intercalation configuration type hydrotalcite film and preparation method thereof
Technical field
The present invention relates to a kind of highly-adherent super-hydrophobic double-functional intercalation configuration type hydrotalcite thin-film material and preparation method thereof.Be specifically related to a kind of anion intercalated hydrotalcite film of longer chain fatty acid salt surfactant on the aluminium base and preparation method thereof that is grown in.
Background technology
Houghite (LDHs) is also referred to as di-hydroxyl composite metal oxidate, is a kind of anionic clay, and its chemical general formula is [M II 1-xM III x(OH) 2] X+(A N-) X ' nYH 2O, wherein M IIAnd M IIIBe respectively divalence and trivalent metal cation, be positioned on the main body laminate; A N-Be interlayer anion; X is M III/ (M II+ M III) molar ratio; Y is the number of middle water molecule.LDHs has the adjustable sex change of laminate structure, laminate element and the interchangeability of interlayer anion.This special property that shows on chemistry and structure not only makes it have ion-exchange performance, all has in many fields such as catalysis, absorption, ion-exchange, electricity material, optical material, biosensor techniques very widely and uses.
Ion exchange method is to utilize the interchangeability of LDHs interlayer anion, the negatively charged ion of required insertion and the interlayer anion of LDHs presoma is exchanged, thereby obtain target LDHs intercalation product.By ion-exchange, can prepare the houghite class material of many functionalization.Studies show that some common anionic exchange capacities are in proper order: CO 3 2-＞SO 4 2-＞HPO 4 2-＞F -＞Cl -＞B (OH) 4 -＞NO 3-Preparing intercalation LDHs by ion exchange method, generally all to adopt nitrate radical or chlorion be precursor.Therefore the LDHs for preparing interlayer anion and be nitrate radical or chlorion has very wide application value.Generally prepare the LDHs that interlayer anion is nitrate radical or chlorion by protection of inert gas.
Ultra-hydrophobicity is with a wide range of applications, and has caused people's common concern in recent years.The contact angle of solid surface and water is called as super hydrophobic surface greater than 150 ° surface, and it generally has high surfaceness and low surface free energy.In general, super hydrophobic surface can prepare by two kinds of methods: a kind of is to make up coarse structure at hydrophobic surface, and another kind is at coarse finishing low surface energy material.It should be noted that for slick solid surface even have minimum surface energy, its contact angle can be above 120 ° yet.Therefore, surpass this contact angle restriction, the structure of surface roughness is a principal element.Studies show that the method for the super-hydrophobic solid surface coarse structure of multiple structure is arranged, as imprint lithography, plasma etching technology, anonizing, phase separation method, template etc.For example at document Angew.Chem.Iht.Ed., 2003 (42): in 800, the method for human Pintsch process phthalocyanine metal complex compounds such as Feng L. is prepared similar lotus leaf by molecular designing and is received the array carbon nano tube of micron dual structure.Document Angew.Chem.Int.Ed. and for example, 2004 (43): in 2012, people such as Feng L. are sprayed on ptfe emulsion on the stainless (steel) wire that the aperture is 115 μ m, and its film is because surface roughening makes hydrophobic performance be enhanced.In order to obtain super hydrophobic surface, with the material of low surface energy the surface is modified also and to be very important.As document J.Am.Chem.Soc., 2005 (127): in 15670, people such as Guo Z. 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.
Because the rolling effect of drop on solid surface can be divided into low adhesive power and high adhesive power super hydrophobic surface to super hydrophobic surface again.High adhesive power super hydrophobic surface not only with the contact angle of water greater than 150 °, and solid surface tilted water droplet still keeps motionless after certain angle.High adhesive power surface extensively is present in occurring in nature, and important effect is played in the survival and development of biology.As the colloid bristle of gecko owing to its foot uniqueness, it can be climbed on vertical wall.The dorsal fin of foot of lizard and seal fish etc. also has very high adhesive power because of its special structure.High adhesive power super hydrophobic surface has many-sided application, as being used for aspects such as free of losses transport of liquid, micro-pipette.More existing bibliographical informations prepare the super hydrophobic surface with high adhesive power.As document Adv.Mater2005 (17): in 1977, it is that the polystyrene film of template preparation has very strong adhesive attraction to water that people such as Jin M. adopt anodised aluminium, does not also tumble even substrate is inverted water droplet.Document J.Mater.Chem.2006 (16): in 122, people such as Nicolas D. utilize the chemical vapor deposition (CVD) method to deposit one deck WSe on glass substrate 2Film, film has very strong adhesive attraction to water.But strictly speaking the contact angle of the film of this method preparation can not be called based superhydrophobic thin films between 135～145 °, and has certain toxicity because film is formed, and therefore on using very big restriction is arranged.
The low surface energy material is effect by surface hydroxyl to the modification on surface, and self-assembly one deck unit molecule organic membrane obtains super hydrophobic surface.Usually mostly the low surface energy material that adopts is fluorochemicals or organosilane.The application of fluorochemicals has very big broken ring effect to physical environment, and the environmental friendliness reagent that must seek other replaces fluorochemical.In addition, the super hydrophobic material by unimolecular layer self-assembly preparation has certain limitation at aspect such as high temperature resistant.
Summary of the invention
The purpose of this invention is to provide a kind of highly-adherent super-hydrophobic double-functional intercalation configuration type hydrotalcite thin-film material and preparation method thereof.The stratiform LDHs film that provides, be to utilize the tradable characteristic of LDHs interlayer anion, with between cheap longer chain fatty acid salt surfactant negatively charged ion interposed layer, its surface has the Nano/micron composite structure, have very superior hydrophobic performance, and the surface there is very strong adhesive attraction to water.Because LDHs laminate and the anionic strong interaction of interlayer longer chain fatty acid salt surfactant, the super hydrophobic material of the high-adhesiveness that obtains has better thermostability.
The highly-adherent super-hydrophobic double-functional intercalation configuration type hydrotalcite thin-film material, the chemical general formula of its rete is:
[Zn 2+ 1-xAl 3+ x(OH) 2] x+(R) x·yH 2O
Wherein R represents C N-1H 2n-1COO -, the span of n is 10～22, is 12～18 preferably; M +Represent monovalent metallic ion K +, Na +0.2≤x≤0.4,0≤y≤2;
The anion intercalated zinc-aluminum gavite thin-film material of this tensio-active agent (is abbreviated as: ZnAl-R-LDHs), the surface has the Nano/micron composite structure, at this composite structure and long-chain fat acid anion under the synergy to the adhesive attraction of water, make the contact angle of film and water droplet reach 140 °～172 °, this film has very strong adhesive attraction to water droplet, substrate is tilted or inversion the also not landing of water droplet on it.
ZnAl-R-LDHs film provided by the invention is by protection of inert gas, and the growth interlayer anion is NO on the aluminium base that surperficial anodic oxidation treatment is crossed 3 -, Cl -Perhaps SO 4 2-The ZnAl-LDHs film, then by ion exchange method, as guest molecule,, obtain the anion intercalated ZnAl-LDHs film of longer chain fatty acid under certain condition with hard soap.
Concrete preparation process is as follows:
A: purity 〉=80%, the thickness aluminium flake between 0.01～1mm is removed surface and oil contaminant with the dehydrated alcohol cleaning, with concentration is that 3～10% sodium hydroxide solution soaks the natural oxidizing layer of removing the surface, clean with deionized water again, with the aluminium flake handled as anode, as negative electrode, the sulphuric acid soln of 0.5～3mol/L is under 1～5A as ionogen at oxidation current with stereotype or stainless steel plate, electrolysis 0.5～5 hour, it is standby to obtain anodised aluminium flake;
B: with solubility divalent zinc salt Zn 2+(Y N+) 2/n(NH 4) nY N+Mol ratio according to 0.05～0.5 is dissolved in and is made into mixing solutions in the deionized water, makes Zn in the mixing solutions 2+Concentration of metal ions is controlled between 0.01～0.5mol/L, is 4.5～8.0 with the pH value of weak ammonia conditioned reaction solution, obtains reaction soln; Y N+Be NO 3 -, Cl -, SO 4 2-In any, that preferable is NO 3 -Or Cl -The preferable pH value scope of reaction soln is 5.5～8.0.
C: the aluminium flake that anodic oxidation treatment is crossed vertically is suspended in the above-mentioned reaction soln, in atmosphere of inert gases, reacts 0.5～96 hour under 25～150 ℃ of temperature.Preferable reaction conditions is 50～130 ℃ of following isothermal reactions 5～72 hours.Take out reacted aluminium base, with deionized water wash 6～7 times, nitrogen purging drying at room temperature, promptly having obtained interlayer anion is Y N-The ZnAl-LDHs film.
D: the ZnAl-LDHs film of preparation vertically is suspended in the longer chain fatty acid salts solution that concentration is 0.01～0.5mol/L, in atmosphere of inert gases, in 25～90 ℃ of following isothermal reactions 2～20 hours, preferable reaction conditions is to react 5～14 hours down at 30～70 ℃, take out reacted substrate, use deionized water wash 6～7 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets the anion intercalated ZnAl-LDHs film of tensio-active agent (ZnAl-R-LDHs film).
The molecular formula of described longer chain fatty acid is C nH 2n-1N +CO 2, N wherein +Represent Na +, K +, n=10～22, preferable is between n=12～18, that best is lauric acid sodium salt C 12H 23NaO 2Or lauric acid sylvite C 12H 23KO 2
Used deionized water is and removes CO in the process 2Deionized water; Described rare gas element is N 2Or Ar.
Adopt day island proper Tianjin XRD-6000 type X-ray diffractometer and the German Bruker Vector22 of company type Fourier transformation infrared spectrometer that sample is carried out qualitative analysis, the results are shown in Figure 1.Curve a is X-ray diffraction (XRD) spectrogram of anodised aluminium flake among the embodiment 1 among Fig. 1.Curve b is ZnAl-NO among the embodiment 1 among Fig. 1 3The XRD spectra of-LDHs film.Except the diffraction peak of aluminium substrate, other diffraction peak can belong to and is (003) of nitrate radical type LDHs, (006), (009) diffraction peak.Curve c is ZnAl-C among the embodiment 1 among Fig. 1 11H 23The XRD spectra of COO-LDHs film according to the ratio of LDHs diffraction peak, can determine that 3.65 ° of X-coordinates, 7.31 °, 10.96 ° pairing diffraction peaks are ZnAl-C 11H 23(003) of COO-LDHs, (006), (009) diffraction peak.Can show that by the XRD data lauric acid negatively charged ion is between interposed layer, and the LDHs that forms has good crystalline structure.Can get ZnAl-C by calculating 11H 23The interlamellar spacing of COO-LDHs is 2.47nm, deducting laminate thickness 0.48nm, to obtain the interlayer channel height be 1.99nm, anionic length 1.57nm compares with sodium laurate, can get the sodium laurate negatively charged ion and be in interlayer region that single-layer portions is staggered arranges perpendicular to the laminate mode, its carboxyl alternately is connected by hydrogen bond with laminate up and down.
With resulting ZnAl-NO among the embodiment 1 3-LDHs film and ZnAl-C 11H 23The COO-LDHs film scrapes from aluminium base, carries out Fourier transform infrared spectroscopy (FT-IR) respectively and characterizes, as shown in Figure 2.Among Fig. 2 a curve as can be seen, behind the intercalation laurate anionic-COO -Asymmetric and symmetrical stretching vibration peak is 1559cm -1And 1420cm -1Be displaced to 1590cm respectively -1And 1410cm -1, and behind the intercalation laurate negatively charged ion at 3443cm -1The place the hydroxyl stretching vibration peak with at 3452cm -1The stretching vibration peak of the laminate hydroxyl at place overlaps, and a broad peak appears in the result, and stronger hydrogen bond and other reduction effects of existence between object laurate negatively charged ion and the LDHs main body laminate is described.
Adopt Japanese HITACHI S-3500N type scanning electronic microscope (SEM) to observe the pattern in film surface and cross section thereof (for more clear all the SEM samples of photograph are all handled through metal spraying).Fig. 3 is the SEM photograph on the aluminium base surface of process anodic oxidation treatment among the embodiment 1.Fig. 4 is the ZnAl-NO of preparation among the embodiment 1 3The SEM photograph of-LDHs film.By photograph as can be seen, the ab face of sexangle tabular LDHs is along having certain included angle direction growth with substrate, and by the Nano/micron composite microstructure that the side and the summit of LDHs flat board constitutes, the plane of Gou Chenging has very high roughness like this.Fig. 5 is the ZnAl-C of preparation among the embodiment 1 11H 23The SEM photograph of COO-LDHs film.Compare ZnAl-C with Fig. 4 11H 23The laminate of COO-LDHs is obviously widened, this is because the tensio-active agent negatively charged ion is easy to limited form a kind of imporosity by hydrophobic interaction in regional at one between the insertion of LDHs interlayer makes the long carbochain of tensio-active agent, thereby causes laminate to broaden.As seen from the figure, ZnAl-C 11H 23The COO-LDHs laminate also keeps arranging perpendicular to the mode of substrate, and the side of the LDHs flat board behind the intercalation and summit still can constitute the Nano/micron composite structure.The long carbochain of LDHs interlayer has constituted the zone that organises, by the similar compatibility principle can with the carbochain effect of laurate negatively charged ion hydrophobic side, and make water-wet side-COO -One end stretches to outside the laminate.So ZnAl-C of preparation 11H 23The COO-LDHs film not only has good hydrophobic performance, and water is had very big adhesion property.
Adopt the German KR ü SS GmbH DSA100 of company type to drip the contact angle and the adhesion property of conformal analysis system testing film.When the test of contact angle, each sample is averaged as last test result different place test 5 times.Testing used water droplet volume is 10 μ L.A figure is that water droplet is at ZnAl-C among Fig. 6 11H 23Optical photograph on the COO-LDHs powder compressing tablet, its contact angle are 85.7 ± 3.1 °.B figure is the highly-adherent super-hydrophobic ZnAl-C that water droplet prepares in embodiment 1 among Fig. 6 11H 23Optical photograph on the COO-LDHs film, its contact angle are 170.6 ± 1.2 °.As seen, because the Nano/micron composite structure of the LDHs film of growth in situ has improved ZnAl-C greatly 11H 23The hydrophobic performance of COO-LDHs.C, d figure are with ZnAl-C among Fig. 6 11H 23The COO-LDHs film substrate tilts or is inverted, and water droplet still adheres on substrate, proves ZnAl-C 11H 23The COO-LDHs film has good adhesive attraction to glassware for drinking water.
The invention has the beneficial effects as follows: the ZnAl-R-LDHs thin-film material surface of preparation has the Nano/micron composite structure, has very superior hydrophobic performance and to the adhesive attraction of water, the contact angle of itself and water droplet is up to 170 °, and water droplet still sticks on the solid surface when substrate tilts or is inverted.Employed hard soap table and activator solution is not fluorine-containing, environmentally safe.Because ZnAl-LDHs laminate and interlayer surface active agent anion strong interaction, the superhydrophobic thin film material of the high-adhesiveness that obtains has better thermostability.The used technology of this law is simple, raw material is easy to get, cost is low, good reproducibility, and the film that makes has good super-hydrophobicity and strong adhesive power.The anion intercalated ZnAl-LDHs based superhydrophobic thin films of this longer chain fatty acid salt surfactant is expected to carry material, biological micro solution pipette etc. as free of losses transport of liquid material, liquid and obtains using.
Description of drawings:
Fig. 1 is aluminium base (a), the ZnAl-NO after the surperficial anodic oxidation for preparing among the embodiment 1 3-LDHs film (b) and ZnAl-C 11H 23The XRD spectra of COO-LDHs film (c);
Fig. 2 is the ZnAl-C of preparation among the embodiment 1 11H 23The corresponding powder (a) of COO-LDHs film, sodium laurate powder (b), ZnAl-NO 3The IR spectrogram of the corresponding powder of-LDHs film (c);
Fig. 3 is the SEM photograph on the aluminium base surface of process anodic oxidation treatment among the embodiment 1;
Fig. 4 is the ZnAl-NO of preparation among the embodiment 1 3-LDHs film SEM photograph;
Fig. 5 is the ZnAl-C of preparation among the embodiment 1 11H 23The SEM photograph of COO-LDHs film;
Fig. 6 is the highly-adherent super-hydrophobic ZnAl-C that water droplet prepares in embodiment 1 11H 23Optical photograph on the COO-LDHs film.
Embodiment:
Below in conjunction with embodiment the present invention further is described:
Embodiment 1:
With purity is 99.5%, and thickness is that the aluminium flake of 0.1mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 5% sodium hydroxide solution soaks the aluminium flake clock and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 1.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 1 hour, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.06mol Zn (NO 3) 26H 2O and 0.24mol NH 4NO 3Be dissolved in 600mL and remove CO 2Deionized water in, the pH with the weak ammonia regulator solution is 7.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, at N 2In the atmosphere, in 45 ℃ of following isothermal reactions 60 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO 3-LDHs film.
The LDHs film that makes vertically is suspended in 0.05mol/L sodium laurate (C 12H 23NaO 2) in the aqueous solution, at N 2In the atmosphere, carry out ion exchange reaction in 30 ℃, take out film after 7 hours, with deionized water wash 6～7 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-C 11H 23The COO-LDHs film.
Resulting ZnAl-NO 3LDHs film and ZnAl-C 11H 23The XRD spectra of COO-LDHs film is seen Fig. 1, and the FT-IR spectrogram is seen Fig. 2, and anodised aluminium base SEM photograph is seen Fig. 3.ZnAl-NO 3-LDHs film SEM photograph is seen Fig. 4, ZnAl-C 11H 23The COO-LDHs film is seen Fig. 5, and water droplet is seen Fig. 6 at the contact angle and the adhesivity optics picture of film surface.Water droplet is 170.6 ± 1.2 ° at the contact angle of film surface.
Embodiment 2:
With purity is 99.5%, and thickness is that the aluminium flake of 0.1mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 5% sodium hydroxide solution soaks the aluminium flake clock and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 1.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 1 hour, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.06mol Zn (NO 3) 26H 2O and 0.24mol NH 4NO 3Be dissolved in 600mL and remove CO 2Deionized water in, the pH with the weak ammonia regulator solution is 6.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, at N 2In the atmosphere, in 45 ℃ of following isothermal reactions 60 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO 3-LDHs film.
The LDHs film that makes vertically is suspended in 0.2mol/L potassium laurate (C 12H 23KO 2) in the aqueous solution, at N 2In the atmosphere, carry out ion exchange reaction in 30 ℃, take out film after 7 hours, with deionized water wash 6～7 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-C 11H 23The COO-LDHs film.Water droplet is 167.8 ± 2.1 ° at the contact angle of film surface.
Embodiment 3:
With purity is 80%, and thickness is that the aluminium flake of 0.1mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 5% sodium hydroxide solution soaks the aluminium flake clock and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 1.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 2 hours, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.12mol Zn (NO 3) 26H 2O and 0.6mol NH 4NO 3Be dissolved in 600mL and remove CO 2Deionized water in, the pH with the weak ammonia regulator solution is 7.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, at N 2In the atmosphere, in 45 ℃ of following isothermal reactions 72 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO 3-LDHs film.
The LDHs film that makes vertically is suspended in 0.05mol/L Sodium tetradecanoate (C 14H 27NaO 2) in the aqueous solution, at N 2In the atmosphere, carry out ion exchange reaction in 30 ℃, take out film after 7 hours, with deionized water wash 6～7 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-C 13H 27The COO-LDHs film.Water droplet is 151.6 ± 1.8 ° at the contact angle of film surface.
Embodiment 4:
With purity is 99.5%, and thickness is that the aluminium flake of 0.4mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 8% sodium hydroxide solution soaks the aluminium flake clock and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 1.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 2 hours, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.12mol Zn (NO 3) 26H 2O and 0.6mol NH 4NO 3Be dissolved in 600mL and remove CO 2Deionized water in, the pH with the weak ammonia regulator solution is 7.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, at N 2In the atmosphere, in 45 ℃ of following isothermal reactions 72 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO 3-LDHs film.
The LDHs film that makes vertically is suspended in 0.2mol/L potassium myristate (C 14H 27KO 2) in the aqueous solution, at N 2In the atmosphere, carry out ion exchange reaction in 30 ℃, take out film after 7 hours, with deionized water wash 6～7 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-C 13H 27The COO-LDHs film.Water droplet is 152.4 ± 1.6 ° at the contact angle of film surface.
Embodiment 5:
With purity is 99.5%, and thickness is that the aluminium flake of 0.1mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 5% sodium hydroxide solution soaks the aluminium flake clock and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 3.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 1 hour, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.06mol Zn (NO 3) 26H 2O and 0.24mol NH 4NO 3Be dissolved in 600mL and remove CO 2Deionized water in, the pH with the weak ammonia regulator solution is 6.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, at N 2In the atmosphere, in 75 ℃ of following isothermal reactions 36 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO 3The LDHs film.
The LDHs film that makes vertically is suspended in 0.05mol/L sodium palmitate (C 16H 31NaO 2) in the aqueous solution, at N 2In the atmosphere, carry out ion exchange reaction in 70 ℃, take out film after 3 hours, with deionized water wash 6～7 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-C 15H 27The COO-LDHs film.Water droplet is 144.2 ± 3.2 ° at the contact angle of film surface.
Embodiment 6:
With purity is 80%, and thickness is that the aluminium flake of 0.4mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 5% sodium hydroxide solution soaks the aluminium flake clock and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 3.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 1 hour, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.12mol Zn (NO 3) 26H 2O and 0.6mol NH 4NO 3Be dissolved in 600mL and remove CO 2Deionized water in, the pH with the weak ammonia regulator solution is 7.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, at N 2In the atmosphere, in 75 ℃ of following isothermal reactions 36 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO 3-LDHs film.
The LDHs film that makes vertically is suspended in 0.2mol/L Palmiticacid potassium (C 16H 31KO 2) in the aqueous solution, at N 2In the atmosphere, carry out ion exchange reaction in 70 ℃, take out film after 3 hours, with deionized water wash 6～7 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-C 15H 27The COO-LDHs film.Water droplet is 160.7 ± 2.6 ° at the contact angle of film surface.

Claims (7)

  1. A highly-adherent super-hydrophobic double-functional intercalation configuration type hydrotalcite film (be abbreviated as: ZnAl-R-LDHs), the chemical general formula of its rete is:
    [Zn 2+ 1-xAl 3+ x(OH) 2] x+(R) x·yH 2O
    Wherein R represents C N-1H 2n-1COO -, the span of n is 10～22; 0.2≤x≤0.4,0≤y≤2;
    This ZnAl-R-LDHs thin-film material, the surface has the Nano/micron composite structure, and the contact angle of itself and water droplet reaches 140 °～172 °, and this film has very strong adhesive attraction to water droplet, tilts or is inverted the substrate that is coated with this film, the not landing of water droplet on it.
  2. 2. ZnAl-R-LDHs film according to claim 1 is characterized in that described C N-1H 2n-1COO -The span of middle n is 12～18.
  3. 3. the preparation method of a ZnAl-R-LDHs film as claimed in claim 1, concrete preparation process is as follows:
    A: purity 〉=80%, the thickness aluminium flake between 0.01～1mm is removed surface and oil contaminant with the dehydrated alcohol cleaning, with concentration is that 3～10% sodium hydroxide solution soaks the natural oxidizing layer of removing the surface, clean with deionized water again, with the aluminium flake handled as anode, as negative electrode, the sulphuric acid soln of 0.5～3mol/L is under 1～5A as ionogen at oxidation current with stereotype or stainless steel plate, electrolysis 0.5～5 hour, it is standby to obtain anodised aluminium flake;
    B: with solubility divalent zinc salt Zn 2+(Y N+) 2/n(NH 4) nY N+Mol ratio according to 0.05～0.5 is dissolved in and is made into mixing solutions in the deionized water, makes Zn in the mixing solutions 2+Concentration of metal ions is controlled between 0.01～0.5mol/L, is 4.5～8.0 with the pH value of weak ammonia conditioned reaction solution, obtains reaction soln; Y N+Be NO 3 -, Cl -, SO 4 2-In any;
    C: the aluminium flake that anodic oxidation treatment is crossed vertically is suspended in the above-mentioned reaction soln, in atmosphere of inert gases, reacts 0.5～96 hour under 25～150 ℃ of temperature; Take out reacted aluminium base, use deionized water wash 6～7 times, at room temperature the nitrogen purging drying obtains the ZnAl-LDHs film;
    D: the ZnAl-LDHs film of preparation vertically is suspended in the longer chain fatty acid salts solution that concentration is 0.01～0.5mol/L, in atmosphere of inert gases, in 25～90 ℃ of following isothermal reactions 2～20 hours, take out reacted substrate, with deionized water wash 6～7 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets the anion intercalated ZnAl-LDHs film of tensio-active agent; The molecular formula of used longer chain fatty acid is C nH 2n-1N +CO 2, N wherein +Represent Na +, K +, n=10～22.
  4. 4. the preparation method of ZnAl-R-LDHs film according to claim 3 is characterized in that the described Y of step B N+Be NO 3 -Or Cl -The pH value of conditioned reaction solution is 5.5～8.0; The reaction conditions of aluminium flake in reaction soln is 50～130 ℃ of following isothermal reactions 5～72 hours among the step C; The reaction conditions of step D is to react 5～14 hours down at 30～70 ℃.
  5. 5. the preparation method of ZnAl-R-LDHs film according to claim 3 is characterized in that the C of step D nH 2n-1N +CO 2In, n=12～18.
  6. 6. the preparation method of ZnAl-R-LDHs film according to claim 3 is characterized in that the C of step D nH 2n-1N +CO 2Be lauric acid sodium salt C 12H 23NaO 2Or lauric acid sylvite C 12H 23KO 2
  7. 7. the preparation method of ZnAl-R-LDHs film according to claim 3 is characterized in that described rare gas element is N 2Or Ar; Used deionized water all is to remove CO in the process 2Deionized water.
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