CN107716252A - A kind of preparation method and its usage of self-clean type super-hydrophobic composite film material - Google Patents
A kind of preparation method and its usage of self-clean type super-hydrophobic composite film material Download PDFInfo
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- CN107716252A CN107716252A CN201710724681.XA CN201710724681A CN107716252A CN 107716252 A CN107716252 A CN 107716252A CN 201710724681 A CN201710724681 A CN 201710724681A CN 107716252 A CN107716252 A CN 107716252A
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- composite film
- film material
- self
- hydrophobic
- clean type
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention belongs to technical field of environment function material preparation, discloses a kind of preparation method and its usage of self-clean type super-hydrophobic composite film material, carries out as steps described below：The super hydrophilic modification of basement membrane：After the dipped hydrophilic solution of basal lamina material, dry, obtain super hydrophilic/underwater superoleophobic composite film material；Super-hydrophobic modification：The super hydrophilic composite membrane prepared is immersed in hydrophobic agent solution and carries out hydrophobic modification, obtains self-clean type super-hydrophobic composite film material.The ultra-hydrophobicity of membrane material is successfully realized by the self-clean type super-hydrophobic composite film material prepared by method of the present invention, can be widely used in dirt-resistant self-cleaning, antifog or anti-icing field.
Description
Technical field
The invention belongs to technical field of environment function material preparation, is related to a kind of system of self-clean type super-hydrophobic composite film material
Preparation Method and application thereof.
Background technology
Self-cleaning is to take off the pollutant of body surface or dust granule automatically under the effect of the external force such as gravity, rainwater, wind-force
The performance for falling and removing.Because lotus leaf has surface that is hydrophobic, not absorbing water, the rainwater fallen on blade face can be because of the work of surface tension
With the formation globule.Therefore, even across a down-pour, the total surface of lotus leaf is to keep drying；In addition, the globule is from lotus leaf
On tumble, the dust granule adsorbed thereon can be removed, reach self clean, spotless effect.On in nature
Self-cleaning material has a lot, such as Chinese scholartree leaf surface, wax gourd surface, water skipper leg, is studied by researcher, it is found that these have
The super hydrophobic surface of self-cleaning property has the material of fine and close micro-nano coarse structure and low-surface-energy, both special structures
Make, turn into two kinds of important thinkings for preparing super hydrophobic material now.
In recent years, it is haze, mist, sandstorm, sand, floating due to the rapid development of industry and the hysteresis of environmental improvement
The weather phenomena such as dirt are serious all the more, and body surface can gradually deposit one layer of trickle particulate contaminants, it is difficult to clean, particularly
Solar panels surface and automotive windshield plate surface, the performance of material in itself is not only influenceed, more causes titanic peril, therefore
Improvement for this pollutant is very urgent, and the phenomenon of " the going out mud without contaminating of lotus leaf " gives the very big spirit of scientific research personnel
Sense, by certain surface treatment so that material also has the self-cleaning function of lotus leaf.
The content of the invention
The present invention is modified by super hydrophilic with two super-hydrophobic steps, and successfully being formed on common material surface has self-cleaning
The composite surface of energy, it is a kind of promising method of tool at the self-cleaning aspect of object.
It is an object of the invention to provide a kind of preparation method of self-clean type super-hydrophobic composite film material, the first super parent of basement membrane
Water is modified：After the dipped hydrophilic solution of basal lamina material, dry, obtain super hydrophilic/underwater superoleophobic composite film material；It is super-hydrophobic to repair
Decorations：The super hydrophilic composite membrane prepared is immersed in hydrophobic agent solution and carries out hydrophobic modification, obtains self-clean type super-hydrophobic composite film
Material；And by a variety of characterization methods, the pattern and hydrophobic performance of composite are disclosed, and be applied to the anti-soil of body surface certainly
Clean, antifog or anti-icing field.
The technical solution adopted by the present invention is：
A kind of preparation method of self-clean type super-hydrophobic composite film material, is carried out as steps described below：
The super hydrophilic modification of step 1, basement membrane：One layer of organotitanate solution is sprayed or soaked in membrane surface, is dried, clearly
Wash, you can obtain super hydrophilic/underwater superoleophobic composite film material；
Step 2, super-hydrophobic modification：By super hydrophilic/underwater superoleophobic composite film material surface spraying in step 1 or it is immersed in
In the hydrophobic agent solution of silicon fluoride, dry, obtain self-clean type super-hydrophobic composite film material.
In step 1, basement membrane is metallic sieve, high temperature resistant filter membrane, metal polyporous material, flame retardant fabric, lucite, tempering
Glass or sheet metal.
The organic titanate is the one or more in tetraethyl titanate, isopropyl titanate or butyl titanate.
The organotitanate solution concentration is 0.1-100mgmL-1。
The solvent of the organotitanate solution is the one or more in hexane, hexamethylene, ethanol, butanol etc..
In step 1, clean as distilled water, hot water or deionized water.
In step 2, described silicon fluoride water-repelling agent is perfluoro decyl trichlorosilane, perfluoro decyl triethoxysilane, complete
One kind in fluorine octyltrichlorosilane or perfluoro capryl triethoxysilane；The concentration of the hydrophobic agent solution of silicon fluoride is 1-
100mg·mL-1。
In step 2, the solvent of the hydrophobic agent solution of described silicon fluoride is hexane or hexamethylene non-polar solven.
Drying in step 2 is drying 0.5-5 hours at 20-80 DEG C.
Self-clean type super-hydrophobic composite film material prepared by the present invention is used for dirt-resistant self-cleaning, antifog or anti-icing field.
Beneficial effects of the present invention are：
(1) base material used in the present invention is extensive, includes the every field such as high polymer material, metal material, wood materials.
(2) self-clean type super-hydrophobic composite film material has the performance such as super-hydrophobic, anti-soil, self-cleaning made from.
(3), can self-cleaning, material waterproofing etc. in material surface in view of the excellent properties of the self-clean type super-hydrophobic composite film material
Field widely uses.
(4) preparation method of the invention is simple and easy, flow is shorter, easy controlled operation, suitable for promoting the use of.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of self-clean type super-hydrophobic composite film material.
Fig. 2 is the static contact angle figure of self-clean type super-hydrophobic composite film material.
Embodiment
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings：
Embodiment 1：
It is 50mgmL in one layer of concentration of metallic sieve surface spraying or leaching-1Tetraethyl titanate ethanol solution in, it is empty
Dried in gas, distilled water, hot water or deionized water cleaning can obtain super hydrophilic/underwater superoleophobic composite film material；
By super hydrophilic/underwater superoleophobic composite film material surface spraying or to be immersed in concentration be 20mgmL-1Perfluoro capryl
3 hours or air drying are dried in the hexane solution of trichlorosilane at 50 DEG C, obtains self-clean type super-hydrophobic composite film material.
Fig. 1 is the scanning electron microscope (SEM) photograph of self-clean type super-hydrophobic composite film material, clearly as can be seen that surface has largely
Micro nano structure.
Fig. 2 be self-clean type super-hydrophobic composite film material static contact angle figure, contact angle 155o, illustrate to have reached super
Hydrophobic performance.
Embodiment 2：
It is 50mgmL to spray or soak one layer of concentration in high temperature resistant filter membrane surface-1Tetraethyl titanate hexane solution in,
Air drying, distilled water, hot water or deionized water cleaning can obtain super hydrophilic/underwater superoleophobic composite film material；
By super hydrophilic/underwater superoleophobic composite film material surface spraying or to be immersed in concentration be 20mgmL-1Perfluoro capryl
3 hours or air drying are dried in the hexane solution of trichlorosilane at 50 DEG C, obtains self-clean type super-hydrophobic composite film material.
Embodiment 3：
It is 0.1mgmL in one layer of concentration of metal polyporous material surface spraying or leaching-1Tetraethyl titanate hexamethylene it is molten
In liquid, air drying, distilled water, hot water or deionized water cleaning can obtain super hydrophilic/underwater superoleophobic composite film material；
By super hydrophilic/underwater superoleophobic composite film material surface spraying or to be immersed in concentration be 100mgmL-1Perfluoro decyl
In the hexane solution of triethoxysilane, 5 hours or air drying are dried at 20 DEG C, obtains self-clean type super-hydrophobic composite film material
Material.
Embodiment 4：
It is 100mgmL in one layer of concentration of flame retardant fabric surface spraying or leaching-1Butyl titanate butanol solution in, it is empty
Dried in gas, distilled water, hot water or deionized water cleaning can obtain super hydrophilic/underwater superoleophobic composite film material；
By super hydrophilic/underwater superoleophobic composite film material surface spraying or to be immersed in concentration be 1mgmL-1Perfluoro capryl three
In the cyclohexane solution of chlorosilane, 0.5 hour or air drying are dried at 80 DEG C, obtains self-clean type super-hydrophobic composite film material
Material.
Embodiment 5：
It is 100mgmL in lucite or safety glass surface spraying or one layer of concentration of leaching-1Isopropyl titanate oneself
Alkane solution, air drying, distilled water, hot water or deionized water cleaning can obtain super hydrophilic/underwater superoleophobic compound film material
Material；
By super hydrophilic/underwater superoleophobic composite film material surface spraying or to be immersed in concentration be 1mgmL-1Perfluoro capryl three
In the hexane solution of Ethoxysilane, 0.5 hour or air drying are dried at 80 DEG C, obtains self-clean type super-hydrophobic composite film material
Material.
Embodiment 6：
It is 20mgmL to spray or soak one layer of concentration in sheet metal surface-1Butyl titanate butanol solution, air
Middle drying, distilled water, hot water or deionized water cleaning can obtain super hydrophilic/underwater superoleophobic composite film material；
By super hydrophilic/underwater superoleophobic composite film material surface spraying or to be immersed in concentration be 10mgmL-1Perfluoro decyl
The hexane solution of trichlorosilane, 3 hours or air drying are dried at 50 DEG C, obtains self-clean type super-hydrophobic composite film material.
Absorption property evaluation is carried out by the following method in specific embodiment in the present invention：, will after contact angle test
Self-clean type super-hydrophobic composite film material carries out antifouling property research.Take the self-clean type super-hydrophobic composite film material prepared, surface
One layer of dust is deposited, then using the mode to drench with rain, surface contaminant is removed, studies the removing situation of surface contaminant.
Claims (10)
1. a kind of preparation method of self-clean type super-hydrophobic composite film material, it is characterised in that carry out as steps described below：
The super hydrophilic modification of step 1, basement membrane：One layer of organotitanate solution is sprayed or soaked in membrane surface, is dried, cleaning, i.e.,
It can obtain super hydrophilic/underwater superoleophobic composite film material；
Step 2, super-hydrophobic modification：By super hydrophilic/underwater superoleophobic composite film material surface spraying in step 1 or it is immersed in fluorine silicon
In the hydrophobic agent solution of alkane, dry, obtain self-clean type super-hydrophobic composite film material.
A kind of 2. preparation method of self-clean type super-hydrophobic composite film material according to claim 1, it is characterised in that step
In 1, basement membrane is metallic sieve, high temperature resistant filter membrane, metal polyporous material, flame retardant fabric, lucite, safety glass or metallic plate
Material.
A kind of 3. preparation method of self-clean type super-hydrophobic composite film material according to claim 1, it is characterised in that step
In 1, the organic titanate is the one or more in tetraethyl titanate, isopropyl titanate or butyl titanate.
A kind of 4. preparation method of self-clean type super-hydrophobic composite film material according to claim 1, it is characterised in that step
In 1, the organotitanate solution concentration is 0.1-100mgmL-1。
A kind of 5. preparation method of self-clean type super-hydrophobic composite film material according to claim 1, it is characterised in that step
In 1, the solvent of the organotitanate solution is the one or more in hexane, hexamethylene, ethanol, butanol etc..
A kind of 6. preparation method of self-clean type super-hydrophobic composite film material according to claim 1, it is characterised in that step
In 1, clean as distilled water, hot water or deionized water.
A kind of 7. preparation method of self-clean type super-hydrophobic composite film material according to claim 1, it is characterised in that step
In 2, described silicon fluoride water-repelling agent is perfluoro decyl trichlorosilane, perfluoro decyl triethoxysilane, perfluoro capryl trichlorine silicon
One kind in alkane or perfluoro capryl triethoxysilane；The concentration of the hydrophobic agent solution of silicon fluoride is 1-100mgmL-1。
A kind of 8. preparation method of self-clean type super-hydrophobic composite film material according to claim 1, it is characterised in that step
In 2, the solvent of the hydrophobic agent solution of described silicon fluoride is hexane or hexamethylene.
A kind of 9. preparation method of self-clean type super-hydrophobic composite film material according to claim 1, it is characterised in that step
Drying in 2 is drying 0.5-5 hours at 20-80 DEG C.
10. the purposes of self-clean type super-hydrophobic composite film material prepared by the method described in claim 1~9 any one, it is special
Sign is, prepared self-clean type super-hydrophobic composite film material is used for into dirt-resistant self-cleaning, antifog or anti-icing field.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710724681.XA CN107716252A (en) | 2017-08-22 | 2017-08-22 | A kind of preparation method and its usage of self-clean type super-hydrophobic composite film material |
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| CN201710724681.XA CN107716252A (en) | 2017-08-22 | 2017-08-22 | A kind of preparation method and its usage of self-clean type super-hydrophobic composite film material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108978200A (en) * | 2018-06-29 | 2018-12-11 | 湖北大学 | A kind of super-hydrophobic and perfusion lubricating fluid smooth type woven fabric preparation method for anti-pollution and freezing |
| CN109338743A (en) * | 2018-09-19 | 2019-02-15 | 宁波捷傲创益新材料有限公司 | A kind of anti misting materials and the preparation method and application thereof |
| CN113249714A (en) * | 2021-05-19 | 2021-08-13 | 许昌学院 | Preparation method of adjustable super-wettability copper surface |
| CN113266121A (en) * | 2021-04-07 | 2021-08-17 | 苟于伟 | Self-cleaning coating film for building outer wall decorative plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1439742A (en) * | 2003-03-27 | 2003-09-03 | 厦门大学 | Metal surface anti-corrosion method based on surface nanometer construct |
| JP2008223003A (en) * | 2006-12-28 | 2008-09-25 | Toto Ltd | Self-cleaning member and coating composition |
| CN105906375A (en) * | 2016-04-20 | 2016-08-31 | 长沙学院 | Preparation method of transparent mesoporous titanium dioxide hydrophobic/ultra-hydrophilic functional thin film |
-
2017
- 2017-08-22 CN CN201710724681.XA patent/CN107716252A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1439742A (en) * | 2003-03-27 | 2003-09-03 | 厦门大学 | Metal surface anti-corrosion method based on surface nanometer construct |
| JP2008223003A (en) * | 2006-12-28 | 2008-09-25 | Toto Ltd | Self-cleaning member and coating composition |
| CN105906375A (en) * | 2016-04-20 | 2016-08-31 | 长沙学院 | Preparation method of transparent mesoporous titanium dioxide hydrophobic/ultra-hydrophilic functional thin film |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108978200A (en) * | 2018-06-29 | 2018-12-11 | 湖北大学 | A kind of super-hydrophobic and perfusion lubricating fluid smooth type woven fabric preparation method for anti-pollution and freezing |
| CN109338743A (en) * | 2018-09-19 | 2019-02-15 | 宁波捷傲创益新材料有限公司 | A kind of anti misting materials and the preparation method and application thereof |
| CN113266121A (en) * | 2021-04-07 | 2021-08-17 | 苟于伟 | Self-cleaning coating film for building outer wall decorative plate |
| CN113249714A (en) * | 2021-05-19 | 2021-08-13 | 许昌学院 | Preparation method of adjustable super-wettability copper surface |
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