CN105419627A - Super-oleophobic coating and preparation method thereof - Google Patents
Super-oleophobic coating and preparation method thereof Download PDFInfo
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- CN105419627A CN105419627A CN201510851648.4A CN201510851648A CN105419627A CN 105419627 A CN105419627 A CN 105419627A CN 201510851648 A CN201510851648 A CN 201510851648A CN 105419627 A CN105419627 A CN 105419627A
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Abstract
The invention discloses a super-oleophobic coating material and a preparation method thereof. A super-oleophobic coating is obtained by establishing a porous coating through an ice template with gas-hpase silicon dioxide nanoparticles and dopamine as structure units and conducting processing through a two-step CVD method. The preparation method is green and environmentally friendly, and can not pollute the environment. The super-strong adhesive capacity of polydopamine is achieved through biological material-dopamine polymerization. The super-oleophobic coating can be applied to metal materials, inorganic nonmetallic materials, polymer materials, natural materials and the like, and a solution of the super-oleophobic coating universal for various different materials is provided.
Description
Technical field
The present invention relates to the technical field of oleophobic coated material, be specifically related to a kind of super oleophobic coating and preparation method thereof.
Background technology
Super oleophobic surface refers to and can reveal to the drip gauge with low surface tension (being usually less than 30mN/m) surface being greater than 150 ° of static contact angles.Due to its excellence to oil and the resist wet behavior of organic solvent, super oleophobic coating can protecting materials be surperficial better, makes it from oil pollution.
From existing result of study, preparing super oleophobic surface is generally have the surface of special microtexture by surface etch technique construction or carry out process to be prepared to fabric, screen cloth, these two kinds of methods are often only applicable to specific material, and being difficult to becomes a kind of super oleophobic surface preparation means being common to differing materials surface.
The super oleophobic coating developed based on coating technology can reduce the demand to equipment, simplifies construction procedure, and is expected to carry out coating when not injury of primary material surface, is expected to develop a kind of super oleophobic coating that can be used for various material surface whereby.
Publication number is the preparation method that the Chinese patent literature of CN103788853A discloses the super two open coat of a kind of urethane/molybdenumdisulphide, first the method prepares urethane/molybdenumdisulphide/nano-scale uneven surface by spraying method, then 1H is passed through, 1H, 2H, 2H – perfluor octyloxy trichlorosilane finish coat, makes coating finally show super two character of dredging.The method need use a large amount of organic solvent, the method for not a kind of environmental protection.
Publication number is the preparation method that CN104353598A Chinese patent literature discloses the transparent super oleophobic coating in a kind of metallic surface, first the method uses sherwood oil and acetone cleaning substrate surface, by polyacrylonitrile and epoxy resin and N after heat drying, N – dimethyl formamide is mixed to get polyacrylonitrile epoxy resin composite solution and is coated to substrate surface, then base material at high temperature being dried 1 hour ~ 5 hours, finally within 1 hour ~ 5 hours, obtaining stable super oleophobic coating by drying under high temperature after polytetrafluoroethylene granule dispersion to substrate surface.The method need at high temperature process coating, has used organic solvent simultaneously, and only proposes the method for the super oleophobic coating of metallic surface preparation, and non-universal surpasses oleophobic coating.
Publication number is the preparation method that the Chinese patent literature of CN104073116A discloses a kind of super two open coat, first the method prepares fluorine containing silane polymers soln, in described fluorine containing silane polymers soln, add tetraethoxy, water and hydrochloric acid to be again hydrolyzed reaction obtained solution, in above-mentioned solution, add nano silicon mix and obtain complex sol, last complex sol on base material described in application, through solidifying the super two open coat of dry acquisition.The method solvent that effects on surface tension force is higher has carried out contact angle test, and according to convention is to the definition of super oleophobic surface in the world, this surface still can not be called as super oleophobic coating.
Publication number is the Chinese patent literature of CN103436138A super-hydrophobic or super pair open coat disclosing a kind of stable transparent and its preparation method and application.Nanoparticle, epoxy resin and solvent carry out blendedly obtaining epoxy resin hydridization solution by the method; Fluorine-containing material and catalyzer are dissolved in obtained fluorine-containing solution in solvent; By epoxy resin hydridization solution spraying to substrate surface, then at high temperature dry 0.5 hour ~ 5 hours, then by fluorine-containing solution spraying to substrate surface dry out solvent under high temperature.The method can apply different surfaces, but owing to employing a large amount of organic solvent, cannot process polymer surfaces, and the existence of a large amount of solvent simultaneously also makes it cannot become a kind of super oleophobic coating process of environmental protection.And in patent, do not relate to the solvent used in test oleophobic property, still its super oleophobic property can not be described well.
US Patent No. 20110157277A1 discloses a kind of super oleophobic and super hydrophobic surface and preparation method thereof.First this patent applies one deck silicon layer at substrate surface, adopts the method for photoengraving to create microscopic pattern on silicon layer, has then prepared super oleophobic coating in applied atop one deck oleophobic coating.The method by surface etch technique construction surface microscopic pattern, need cannot be applicable to differing materials surface.
United States Patent (USP) (application number 61373946) discloses a kind of super oleophobic surface preparation method based on spraying method.This patent is by the metal oxide particle of fluorinated alkyl silane treatment and the dispersion of fluoroelastomer tackiness agent or be dissolved in lower boiling containing in fluorous solvent, by spraying method, dispersion liquid is applied to material surface and prepares super oleophobic coating.But the method uses containing fluorous solvent, can produce great impact to human body and environment.
Summary of the invention
Current technical barrier does not still have a kind of super oleophobic coating technology effectively can be common to various differing materials surface.The present invention is by means of a kind of bioadhesive polymer---and Dopamine HCL provides the free of contamination general super oleophobic coating technology of a kind of environmental protection.
A preparation method for super oleophobic coated material, first mixes aerosil nanoparticle with Dopamine HCL; Porous coating is formed again by being coated on material surface after mixed system oxide treatment; Successively on porous coating, deposit amino silicane coupling agent and silicon fluoride coupling agent finally by two step CVD, obtain super oleophobic coating.
In the inventive method, Dopamine HCL oxidation autohemagglutination must gather Dopamine HCL, and aerosil nanoparticle is bonded in material surface and forms porous coating by poly-Dopamine HCL.Then by two step CVD, first form one deck silicone hydroxyl on porous coating surface, then at chemical grafting treated silicon fluoride coupling agent, thus reduce the surface energy of vesicular structure, obtained super oleophobic coating.The inventive method is common to various material surface, and without the need to etachable material surface; Simple to operate, environmental protection; The oleophobic excellent property of obtained super oleophobic coating.
Present method is implemented by following two kinds of modes, and the raw materials of mode (a) is dispersion liquid, amino silicane coupling agent and silicon fluoride coupling agent that aerosil nanoparticle/dopamine hydrochloride and TrisHCl damping fluid are made into; The raw materials of mode (b) is dispersion liquid, NaIO that aerosil nanoparticle/dopamine hydrochloride and water are made into
4the aqueous solution, amino silicane coupling agent and silicon fluoride coupling agent.
As preferably, the preparation method of super oleophobic coated material, comprises the following steps:
(a1) aerosil nanoparticle dispersion being prepared silica dispersions in TrisHCl damping fluid, continuing toward wherein adding dopamine hydrochloride, after dopamine hydrochloride dissolves, obtain dispersion liquid A1;
(a2) dispersion liquid A1 obtains dispersion liquid B1 in atmosphere after reaction;
(a3) dispersion liquid B1 is applied to material surface and obtains porous coating through lyophilize;
(a4) successively on porous coating, deposit amino silicane coupling agent and silicon fluoride coupling agent by two step CVD, obtain super oleophobic coating;
Or,
(b1) aerosil nanoparticle dispersion is prepared silica dispersions in water, in dispersion liquid, add dopamine hydrochloride, dopamine hydrochloride obtains dispersion liquid A2 after dissolving;
(b2) by NaIO
4be dissolved in the water and obtain NaIO
4aqueous solution C;
(b3) by dispersion liquid A2 and NaIO
4aqueous solution C makes Dopamine HCL at room temperature react for some time after mixing and obtains dispersion liquid B2;
(b4) porous coating is obtained through lyophilize after dispersion liquid B2 being applied to material surface;
(b5) successively on porous coating, deposit amino silicane coupling agent and silicon fluoride coupling agent by two step CVD, obtain super oleophobic coating.
Dopamine hydrochloride is oxidized under alkaline or neutral conditions and forms poly-Dopamine HCL, by means of the effect of aerosil nanoparticle, makes the porous coating that the bonding one deck of material surface is formed by aerosil nanoparticle and poly-Dopamine HCL.Dopamine HCL and aerosil nanoparticle have synergy, the poly-bonding aerosil nanoparticle of Dopamine HCL, and by means of ice template, the mode making buildings to be similar to " Steel Concrete " builds porous coating at material surface, is conducive to the deposition effect of the coupling agent improving follow-up CVD by the porous coating of which framework.
In embodiment (a), dopamine hydrochloride is oxidized in the aerosil nanoparticle system of alkalescence, the oxygenant adopted is oxygen, after dopamine hydrochloride oxidation autohemagglutination completes, the bonding system (dispersion liquid B1) formed is coated on material surface and forms porous coating.In embodiment (b), dopamine hydrochloride is oxidized in the aerosil nanoparticle system of neutrality, adopts strong oxidizer NaIO
4, after oxidation autohemagglutination completes, the bonding system (dispersion liquid B2) formed is coated on material surface and forms porous coating.The operation of two kinds of embodiments is all comparatively simple, without the need to carrying out the process such as polishing to material surface, little to material damage, is common to various differing materials surface, and good at the adhesive effect of material surface.
The specific surface area of described aerosil nanoparticle is 10m
2/ g ~ 1000m
2/ g, in described dispersion liquid A1 and dispersion liquid A2, the mass concentration of aerosil is 0.01% ~ 10%; The concentration of described dopamine hydrochloride is 0.05mg/mL ~ 20mg/mL.
As preferably, the concentration of aerosil nanoparticle is 0.1% ~ 2%.The aerosil nanoparticle of described specific surface area and mass concentration contributes to forming good porous coating.If aerosil nanoparticle concentration is too low, then do not become perfect coating, if concentration is too high, then can cause dispersion liquid B
1or B
2the coacervate that middle formation is larger, produces precipitation, affects the use of dispersion liquid.
As preferably, the concentration of dopamine hydrochloride is 0.1mg/mL ~ 5mg/mL, if the concentration of dopamine hydrochloride is too low, then cannot produce enough poly-Dopamine HCLs, causes the coating imperfection formed, and for the control to cost, the concentration of dopamine hydrochloride is unsuitable too high.
Described TrisHCl buffer concentration is 10mM, pH is 8.0 ~ 9.0.
In embodiment (b), described NaIO
4the concentration of the aqueous solution (solution C) is 50mM ~ 5000mM, as preferably, and NaIO
4the concentration of the aqueous solution is 50mM ~ 1000mM.
NaIO described in step (b2)
4naIO in aqueous solution C
4concentration be 50mM ~ 5000mM; In step (b3), dispersion liquid A2 and NaIO
4the volume ratio of aqueous solution C is 100:1 ~ 1:1.
As preferably, the volume ratio of dispersion liquid A2 and solution C is 20:1 ~ 1:1.
The reaction times of step (a2) and the Dopamine HCL described in (b3) is 12 hours ~ 50 hours, and as preferably, the reaction times is 18 hours ~ 30 hours.
Obtained dispersant B 1 and dispersant B 2 after autohemagglutination completes, are carried out the process such as follow-up coating and vesicular structure formation by the Dopamine HCL oxidation of step (a2) and (b3).
After dispersant B 1 and dispersant B 2 are coated on surface, in order to build vesicular structure at material surface fast, need to carry out subzero treatment to step (a3) and (b4), as preferably, the treatment temp of step (a3) and (b4) below 0 DEG C, and is carried out under vacuum.
As preferably, the treatment temp of step (a3) and (b4) is-80 DEG C ~ 0 DEG C.
At such a temperature, the treatment time is more than 5 minutes, and as preferably, the subzero treatment time is 30 minutes ~ 96 hours.Under described temperature range, the water in dispersion liquid B1 and dispersion liquid B2 forms ice, by means of ice template, makes Nano particles of silicon dioxide and poly-Dopamine HCL build porous coating at material surface, and in this temperature range, rejects ice, contribute to the drying of porous coating.But consider equipment and cost factor, treatment temp is unsuitable too low.
In step (a3) and step (b4), the consumption being applied to material surface of dispersion liquid B1 and dispersion liquid B2 is 5 μ L/cm
2~ 200 μ L/cm
2.
If apply dispersion liquid measure very little, then finally cannot form perfect vesicular structure, if it is too many to apply dispersion liquid, then cause coating too thick, cost is too high and impracticable.
All porous coating is built, as metallic substance, ceramic, polymer materials or natural materials by the inventive method in solid-state material surface under normal temperature and pressure.
After material surface builds porous coating, by two step chemical depositions by respectively by amino silicane coupling agent and silane coupling agent on porous coating surface, as preferably, step (a4) and two step CVD described in step (b5), comprise the following steps:
Step (1): the first step CVD process: adopt CVD to deposit amino silicane coupling agent in the porous coating of step (a3) or step (b4), the consumption of described amino silicane coupling agent is 100 μ L ~ 5L, the first step CVD treatment temp is 15 DEG C ~ 80 DEG C, and the first step CVD treatment time is 12 hours ~ 120 hours;
Step (2): second step CVD process: adopt the surface deposition silicon fluoride coupling agent of CVD after step (1) process, the consumption of silicon fluoride coupling agent is 100 μ L ~ 5L; Second step CVD treatment temp is 15 DEG C ~ 80 DEG C, and the second step CVD treatment time is 3 hours ~ 120 hours.
The first step CVD process is by the amino on silane coupling agent and the reaction of poly-Dopamine HCL, and hydrolysis generation silicone hydroxyl occurs its oxyethyl group or methoxyl group etc. simultaneously, for the process of next step silane coupling agent provides platform.Silicon fluoride coupling agent is reacted silicon fluoride coupling agent chemical graft the most at last by the silicone hydroxyl that hydrolysis and the first step are formed and, in vesicular structure surface, effectively reduces the surface energy of vesicular structure by second step CVD process.
Described amino silicane coupling agent is one or more in aminopropyl triethoxysilane coupling agent, aminopropyl trimethoxysilane coupling agent, aminopropyl trichlorosilane, N – (β – aminoethyl) – γ – aminopropyl triethoxysilane, N – (β – aminoethyl) – γ – aminopropyl trimethoxysilane, N – (β – aminoethyl) – γ – aminopropyl trichlorosilane.For the consideration to cost, be preferably aminopropyl triethoxysilane or N – (β – aminoethyl) – γ – aminopropyl triethoxysilane.
Described silicon fluoride coupling agent is 1H, 1H, 2H, 2H – perfluoro decyl triethoxyl silane, 1H, 1H, 2H, 2H – perfluoro decyl Trimethoxy silane, 1H, 1H, 2H, 2H – perfluoro decyl trichlorosilane, 1H, 1H, 2H, 2H – perfluoro capryl triethoxyl silane, 1H, 1H, 2H, 2H – perfluoro capryl Trimethoxy silane, 1H, 1H, 2H, one or more in 2H – perfluoro capryl trichlorosilane, in order to make the oleophobic effects optimization of coating, be preferably the more 1H of Oil repellent, 1H, 2H, 2H – perfluoro decyl triethoxyl silane, 1H, 1H, 2H, 2H – perfluoro decyl Trimethoxy silane or 1H, 1H, 2H, 2H – perfluoro decyl trichlorosilane.
Super oleophobic coating prepared by the preparation method that the present invention also comprises described super oleophobic coating.This super oleophobic coating all shows for the drop of surface tension from 75mN/m to 20mN/m the static contact angle being greater than 150 °, and drop can slip away easily from coatingsurface.
Technique effect of the present invention is:
1, simple, the environmental protection of the preparation method of general super oleophobic coating of the present invention and coating.Be polymerized the bonding aerosil nanoparticle of poly-Dopamine HCL obtained by Dopamine HCL, by means of ice template, be similar to " Steel Concrete " with one and make the mode of buildings to build porous coating.
2, the adhesive capacity that the present invention utilizes Dopamine HCL superpower makes coating adhere to different material surfaces, and these materials comprise metallic substance, ceramic, polymer materials and natural material etc.By this biomaterial---the use of Dopamine HCL, can avoid damaging raw-material surface.3, two step CVD provided by the invention can improve the oleophobic effects on surface.
Accompanying drawing explanation
Fig. 1 is the obtained super oleophobic coating of the embodiment of the present invention 1 and the photo of olive oil droplet in coating.
Fig. 2 is that the obtained super oleophobic coating of the embodiment of the present invention 1 is to the contact angle of different surfaces tension force drop.
Fig. 3 is the obtained super oleophobic coating of the embodiment of the present invention 11 and the photo of olive oil droplet in coating.
Fig. 4 is the obtained super oleophobic coating of the embodiment of the present invention 12 and n-hexadecane (light color) and water droplet (dark color) photo droplet in coating.
Embodiment
If no special instructions, the various raw materials in the present invention are commercially available prod; Or can obtain according to preparation method general in this area.Unless otherwise indicated or illustrate, technical term used herein and this area routine term is identical.
Embodiment 1
By magnetic agitation and ultrasonic disperse, by 0.1g aerosil nanoparticle, (specific surface area is 300m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10gTrisHCl damping fluid, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 0.5mg/mL.By above-mentioned dispersion liquid connecting the stirring of open to atmosphere situation lower magnetic force, reacting and within 24 hours, making Dopamine HCL aggregate into poly-Dopamine HCL.
According to 60 μ L/cm
2consumption dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-80 DEG C.Afterwards, coating carries out two step CVD process: the first step, carries out CVD process 24 hours at 25 DEG C with 1mL aminopropyl triethoxysilane; Second step, with 300 μ L1H at 25 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 24 hours.Final obtained super oleophobic coating (Fig. 1).
The numerical value (Fig. 2) of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 2
By magnetic agitation and ultrasonic disperse, by 0.3g aerosil nanoparticle, (specific surface area is 100m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10gTrisHCl damping fluid, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 1mg/mL.By above-mentioned dispersion liquid connecting the stirring of open to atmosphere situation lower magnetic force, reacting and within 24 hours, making Dopamine HCL aggregate into poly-Dopamine HCL.
According to 60 μ L/cm
2consumption dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-80 DEG C.Afterwards, coating carries out two step CVD process: the first step, carries out CVD process 24 hours at 25 DEG C with 1mL aminopropyl triethoxysilane; Second step, with 300 μ L1H at 25 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 24 hours.Final obtained super oleophobic coating.
The numerical value of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement, similar with Fig. 2.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 3
By magnetic agitation and ultrasonic disperse, by 0.3g aerosil nanoparticle, (specific surface area is 200m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10gTrisHCl damping fluid, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 0.5mg/mL.By above-mentioned dispersion liquid connecting the stirring of open to atmosphere situation lower magnetic force, reacting and within 24 hours, making Dopamine HCL aggregate into poly-Dopamine HCL.
According to 20 μ L/cm
2consumption dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-40 DEG C.Afterwards, coating carries out two step CVD process: the first step, carries out CVD process 24 hours at 40 DEG C with 1mL aminopropyl triethoxysilane; Second step, with 300 μ L1H at 40 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 24 hours.Final obtained super oleophobic coating.
The numerical value of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement, similar with Fig. 2.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 4
By magnetic agitation and ultrasonic disperse, by 0.05g aerosil nanoparticle, (specific surface area is 400m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10gTrisHCl damping fluid, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 0.2mg/mL.By above-mentioned dispersion liquid connecting the stirring of open to atmosphere situation lower magnetic force, reacting and within 18 hours, making Dopamine HCL aggregate into poly-Dopamine HCL.
According to 50 μ L/cm
2consumption dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-40 DEG C.Afterwards, coating carries out two step CVD process: the first step, carries out CVD process 36 hours at 25 DEG C with 2mL aminopropyl triethoxysilane; Second step, with 500 μ L1H at 25 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 24 hours.Final obtained super oleophobic coating.
The numerical value of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement, similar with Fig. 2.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 5
By magnetic agitation and ultrasonic disperse, by 0.1g aerosil nanoparticle, (specific surface area is 300m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10gTrisHCl damping fluid.Add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 0.5mg/mL, by dispersion liquid connecting the stirring of open to atmosphere situation lower magnetic force, reacting and within 48 hours, making Dopamine HCL aggregate into poly-Dopamine HCL.
According to 10 μ L/cm
2amount dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-80 DEG C.Afterwards, coating carries out two step CVD process: the first step, carries out CVD process 24 hours at 25 DEG C with 1mL aminopropyl triethoxysilane; Second step, with 300 μ L1H at 25 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 24 hours.Final obtained super oleophobic coating.
The numerical value of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement, similar with Fig. 2.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 6
By magnetic agitation and ultrasonic disperse, by 0.1g aerosil nanoparticle, (specific surface area is 400m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10g water, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 0.5mg/mL.Take a certain amount of NaIO
4, and be dissolved in the water and prepare the NaIO of 300mM
4the aqueous solution.By composite dispersion liquid and NaIO
4the aqueous solution is with after volume ratio 10:3 mixing, and magnetic agitation, reacts 24 hours.
According to 60 μ L/cm
2consumption dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-80 DEG C.Afterwards, coating carries out two step CVD process: the first step, carries out CVD process 24 hours at 25 DEG C with 1mL aminopropyl triethoxysilane; Second step, with 300 μ L1H at 25 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 24 hours.Final obtained super oleophobic coating.
The numerical value of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement, similar with Fig. 2.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 7
By magnetic agitation and ultrasonic disperse, by 0.5g aerosil nanoparticle, (specific surface area is 100m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10g water, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 1mg/mL.Take a certain amount of NaIO
4, and be dissolved in the water and prepare the NaIO of 300mM
4the aqueous solution.By composite dispersion liquid and NaIO
4the aqueous solution is with after volume ratio 1:1 mixing, and magnetic agitation, reacts 24 hours.
According to 30 μ L/cm
2consumption dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-80 DEG C.Afterwards, coating carries out two step CVD process: the first step, carries out CVD process 24 hours at 25 DEG C with 1mL aminopropyl triethoxysilane; Second step, with 300 μ L1H at 25 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 24 hours.Final obtained super oleophobic coating.
The numerical value of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement, similar with Fig. 2.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 8
By magnetic agitation and ultrasonic disperse, by 0.1g aerosil nanoparticle, (specific surface area is 200m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10g water, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 2mg/mL.Take a certain amount of NaIO
4, and be dissolved in the water and prepare the NaIO of 100mM
4the aqueous solution.By composite dispersion liquid and NaIO
4the aqueous solution is with after volume ratio 10:3 mixing, and magnetic agitation, reacts 24 hours.
According to 60 μ L/cm
2consumption dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-80 DEG C.Afterwards, coating carries out two step CVD process: the first step, carries out CVD process 48 hours at 25 DEG C with 2mL aminopropyl triethoxysilane; Second step, with 500 μ L1H at 25 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 24 hours.Final obtained super oleophobic coating.
The numerical value of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement, similar with Fig. 2.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 9
1, by magnetic agitation and ultrasonic disperse, by 0.1g aerosil nanoparticle, (specific surface area is 400m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10g water.
2, in above-mentioned dispersion liquid, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 0.5mg/mL.
3, a certain amount of NaIO is taken
4, and be dissolved in the water and prepare the NaIO of 300mM
4the aqueous solution.
4, by composite dispersion liquid and NaIO
4the aqueous solution is with after volume ratio 10:3 mixing, and magnetic agitation, reacts 24 hours.
5, according to 60 μ L/cm
2consumption dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-80 DEG C.
6, the coating after lyophilize carries out two step CVD process: the first step, carries out CVD process 24 hours at 25 DEG C with 1mL aminopropyl triethoxysilane; Second step, with 300 μ L1H at 25 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 24 hours.Final obtained super oleophobic coating.
The numerical value of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement, similar with Fig. 2.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 10
By magnetic agitation and ultrasonic disperse, by 0.05g aerosil nanoparticle, (specific surface area is 100m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10g water, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 0.05mg/mL.Take a certain amount of NaIO
4, and be dissolved in the water and prepare the NaIO of 50mM
4the aqueous solution.By composite dispersion liquid and NaIO
4the aqueous solution is with after volume ratio 100:1 mixing, and magnetic agitation, reacts 30 hours.
According to 40 μ L/cm
2consumption dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-20 DEG C.Afterwards, coating carries out two step CVD process: the first step, carries out CVD process 24 hours at 30 DEG C with 1mL aminopropyl triethoxysilane; Second step, with 100 μ L1H at 30 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 40 hours.Final obtained super oleophobic coating.
The numerical value of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement, similar with Fig. 2.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 11
By magnetic agitation and ultrasonic disperse, by 0.1g aerosil nanoparticle, (specific surface area is 400m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10g water, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 0.5mg/mL.Take a certain amount of NaIO
4, and be dissolved in the water and prepare the NaIO of 300mM
4the aqueous solution.By composite dispersion liquid and NaIO
4the aqueous solution is with after volume ratio 10:3 mixing, and magnetic agitation, reacts 24 hours.
According to 60 μ L/cm
2consumption dispersion liquid is applied to aluminium flake surface, carry out lyophilize after it is freezing in-80 DEG C.Afterwards, coating carries out two step CVD process: the first step, carries out CVD process 24 hours at 25 DEG C with 1mL aminopropyl triethoxysilane; Second step, with 300 μ L1H at 25 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 24 hours.Final obtained super oleophobic coating (Fig. 3).
The numerical value of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement, similar with Fig. 2.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 12
By magnetic agitation and ultrasonic disperse, by 0.1g aerosil nanoparticle, (specific surface area is 400m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10g water, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 0.5mg/mL.Take a certain amount of NaIO
4, and be dissolved in the water and prepare the NaIO of 300mM
4the aqueous solution.By composite dispersion liquid and NaIO
4the aqueous solution is with after volume ratio 10:3 mixing, and magnetic agitation, reacts 24 hours.
According to 60 μ L/cm
2consumption dispersion liquid is applied to wood surface, carry out lyophilize after it is freezing in-80 DEG C.Afterwards, coating carries out two step CVD process: the first step, carries out CVD process 24 hours at 25 DEG C with 1mL aminopropyl triethoxysilane; Second step, with 300 μ L1H at 25 DEG C, 1H, 2H, 2H-perfluoro decyl triethoxyl silane carries out CVD process 24 hours.Final obtained super oleophobic coating (Fig. 4).
The numerical value of different surfaces tension force drop at the contact angle of super oleophobic surface can be recorded with contact angle measurement, similar with Fig. 2.The drop of surface tension in 73mN/m to 23mN/m scope all can show the contact angle being greater than 150 ° in coating.After coating inclination certain angle, drop all can free landing.
Embodiment 13
Dispersion liquid, as embodiment 12, can be applied to the ceramic surfaces such as the polymer materials such as silicon rubber, polymethylmethacrylate and pottery, all can obtain super oleophobic coating by other steps in step b5.
Embodiment 14
Other steps are as embodiment 1, in step b5 during the first step CVD process, aminopropyl triethoxysilane can change other amino silicane coupling agents into, as aminopropyl trimethoxysilane coupling agent, aminopropyl trichlorosilane, N – (β – aminoethyl) – γ – aminopropyl triethoxysilane, N – (β – aminoethyl) – γ – aminopropyl trimethoxysilane, N – (β – aminoethyl) – γ – aminopropyl trichlorosilane etc., super oleophobic coating all can be obtained.
Embodiment 15
Other steps as embodiment 1, in step 5 during second step CVD process, 1H, 1H, 2H, 2H – perfluoro decyl triethoxyl silane can be changed to other silicon fluoride coupling agents, as 1H, 1H, 2H, 2H – perfluoro decyl Trimethoxy silane, 1H, 1H, 2H, 2H – perfluoro decyl trichlorosilane, 1H, 1H, 2H, 2H – perfluoro capryl triethoxyl silane, 1H, 1H, 2H, 2H – perfluoro capryl Trimethoxy silane, 1H, 1H, 2H, 2H – perfluoro capryl trichlorosilanes etc., all can obtain super oleophobic coating.
Comparative example 1
By magnetic agitation and ultrasonic disperse, by 0.1g aerosil nanoparticle, (specific surface area is 300m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10gTrisHCl damping fluid, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 0.5mg/mL.By above-mentioned dispersion liquid connecting the stirring of open to atmosphere situation lower magnetic force, reacting and within 24 hours, making Dopamine HCL aggregate into poly-Dopamine HCL.
According to 60 μ L/cm
2consumption dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-80 DEG C.Record the contact angle of coating to all drops with contact angle measurement and be 0 DEG C.
Comparative example 2
By magnetic agitation and ultrasonic disperse, by 0.1g aerosil nanoparticle, (specific surface area is 300m
2/ g) be scattered in the dispersion liquid preparing stable homogeneous in 10gTrisHCl damping fluid, add dopamine hydrochloride and be made into the composite dispersion liquid that dopamine hydrochloride concentration is 0.5mg/mL.By above-mentioned dispersion liquid connecting the stirring of open to atmosphere situation lower magnetic force, reacting and within 24 hours, making Dopamine HCL aggregate into poly-Dopamine HCL.
According to 60 μ L/cm
2consumption dispersion liquid is applied to glass surface, carry out lyophilize after it is freezing in-80 DEG C.Carry out as after the first step CVD process in embodiment 1 to coating aminopropyl triethoxysilane, the contact angle of coating is measured with contact angle measurement, the drip gauge that a discovery coating effects on surface tension force is greater than 50mN/m reveals the contact angle being greater than 150 °, and coating does not show excess of export oleophobic property after the first step CVD process.
Claims (10)
1. a preparation method for super oleophobic coated material, is characterized in that, is first mixed with Dopamine HCL by aerosil nanoparticle; Porous coating is formed again by being coated on material surface after mixed system oxide treatment; Successively on porous coating, deposit amino silicane coupling agent and silicon fluoride coupling agent finally by two step CVD, obtain super oleophobic coating.
2. the preparation method of super oleophobic coated material as claimed in claim 1, is characterized in that, comprise the following steps:
(a1) aerosil nanoparticle dispersion being prepared silica dispersions in TrisHCl damping fluid, continuing toward wherein adding dopamine hydrochloride, after dopamine hydrochloride dissolves, obtain dispersion liquid A1;
(a2) dispersion liquid A1 obtains dispersion liquid B1 in atmosphere after reaction;
(a3) dispersion liquid B1 is applied to material surface and obtains porous coating through lyophilize;
(a4) successively on porous coating, deposit amino silicane coupling agent and silicon fluoride coupling agent by two step CVD, obtain super oleophobic coating;
Or,
(b1) aerosil nanoparticle dispersion is prepared silica dispersions in water, in dispersion liquid, add dopamine hydrochloride, dopamine hydrochloride obtains dispersion liquid A2 after dissolving;
(b2) by NaIO
4be dissolved in the water and obtain NaIO
4aqueous solution C;
(b3) by dispersion liquid A2 and NaIO
4aqueous solution C makes Dopamine HCL at room temperature react for some time after mixing and obtains dispersion liquid B2;
(b4) porous coating is obtained through lyophilize after dispersion liquid B2 being applied to material surface;
(b5) successively on porous coating, deposit amino silicane coupling agent and silicon fluoride coupling agent by two step CVD, obtain super oleophobic coating.
3. the preparation method of super oleophobic coated material as claimed in claim 2, it is characterized in that, the specific surface area of described aerosil nanoparticle is 10m
2/ g ~ 1000m
2/ g, in described dispersion liquid A1 and dispersion liquid A2, the mass concentration of aerosil is 0.01% ~ 10%; The concentration of described dopamine hydrochloride is 0.05mg/mL ~ 20mg/mL.
4. the preparation method of super oleophobic coated material as claimed in claim 2, it is characterized in that, described TrisHCl buffer concentration is 10mM, pH is 8.0 ~ 9.0.
5. the preparation method of super oleophobic coated material as claimed in claim 2, is characterized in that, the NaIO described in step (b2)
4naIO in aqueous solution C
4concentration be 50mM ~ 5000mM; In step (b3), dispersion liquid A2 and NaIO
4the volume ratio of aqueous solution C is 100:1 ~ 1:1.
6. the preparation method of super oleophobic coated material as claimed in claim 2, is characterized in that, in step (a3) and step (b4), the consumption being applied to material surface of dispersion liquid B1 and dispersion liquid B2 is 5 μ L/cm
2~ 200 μ L/cm
2.
7. the preparation method of super oleophobic coated material as claimed in claim 2, it is characterized in that, step (a4) and two step CVD described in step (b5), comprise the following steps:
Step (1): the first step CVD process: adopt CVD to deposit amino silicane coupling agent in the porous coating of step (a3) or step (b4), the consumption of described amino silicane coupling agent is 100 μ L ~ 5L, the first step CVD treatment temp is 15 DEG C ~ 80 DEG C, and the first step CVD treatment time is 12 hours ~ 120 hours;
Step (2): second step CVD process: adopt the surface deposition silicon fluoride coupling agent of CVD after step (1) process, the consumption of silicon fluoride coupling agent is 100 μ L ~ 5L; Second step CVD treatment temp is 15 DEG C ~ 80 DEG C, and the second step CVD treatment time is 3 hours ~ 120 hours.
8. the preparation method of super oleophobic coated material as claimed in claim 7, it is characterized in that, described amino silicane coupling agent is one or more in aminopropyl triethoxysilane coupling agent, aminopropyl trimethoxysilane coupling agent, aminopropyl trichlorosilane, N – (β – aminoethyl) – γ – aminopropyl triethoxysilane, N – (β – aminoethyl) – γ – aminopropyl trimethoxysilane, N – (β – aminoethyl) – γ – aminopropyl trichlorosilane.
9. the preparation method of super oleophobic coated material as claimed in claim 7, it is characterized in that, described silicon fluoride coupling agent is 1H, 1H, 2H, 2H – perfluoro decyl triethoxyl silane, 1H, 1H, 2H, 2H – perfluoro decyl Trimethoxy silane, 1H, 1H, 2H, 2H – perfluoro decyl trichlorosilane, 1H, 1H, 2H, 2H – perfluoro capryl triethoxyl silane, 1H, 1H, 2H, 2H – perfluoro capryl Trimethoxy silane, 1H, one or more in 1H, 2H, 2H – perfluoro capryl trichlorosilane.
10. the super oleophobic coated material that as described in any one of claim 1-9 prepared by the preparation method of super oleophobic coated material.
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