CN104085853A - Method for manufacturing micro-nanometer structure super-hydrophobic anti-icing thin film on surface of adhesive tape - Google Patents
Method for manufacturing micro-nanometer structure super-hydrophobic anti-icing thin film on surface of adhesive tape Download PDFInfo
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- CN104085853A CN104085853A CN201410337118.3A CN201410337118A CN104085853A CN 104085853 A CN104085853 A CN 104085853A CN 201410337118 A CN201410337118 A CN 201410337118A CN 104085853 A CN104085853 A CN 104085853A
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Abstract
The invention discloses a method for manufacturing a micro-nanometer structure super-hydrophobic anti-icing thin film on the surface of adhesive tape. The method includes the steps that buffer material is prepared, the buffer material and PVDF powder are mixed, and the mixed powder adheres to the surface of the adhesive tape; then, nanometer rods distributed in a ZnO array are manufactured with a hydrothermal method. The micro-nanometer structure thin film has a very good gas-solid ratio on the surface of the adhesive tape, the contact angle is 155 degrees, a very good super-hydrophobic effect can be achieved, and the thin film can be flatly laid on the surface of a substrate needing hydrophobic anti-icing operation. The method is easy to achieve, low in cost, easy to operate, short in period and capable of being used for large-scale production.
Description
Technical field
The present invention the invention belongs to surface chemistry field, more particularly, refers to a kind of method of making the super-hydrophobic anti-ina thin film of micro nano structure at tape surface.
Background technology
The preparation method on anti-icing surface has a lot, comprises hydro-thermal method, electron beam lithography etc.These methods all have very high requirement to material, and for example in preparation process, base material needs withstand high temperatures, seldom have method to mention to avoid pyroprocess to prepare super-hydrophobic, anti-icing surface.In recent years, there are some documents by preparing micro nano structure at steel plate or silicon chip surface.But in this preparation process, all need substrate to carry out high-temperature process, for example surface of steel plate will do the high temperature that crystal seed just needs 400 DEG C of left and right, and the substrate of ion etching technology need to tolerate the high temperature of degree more than 1,000, under such condition, general macromolecular material can not bear.And these technology all need highly energy-consuming, expensive, so this has all limited these methods greatly in industrial application.For the problem of above-mentioned existence, the present invention accomplished not need main equipment, simply, easily realize.
Summary of the invention
For current in ice-covering-proof field existing problem, the present invention relates to a kind of brand-new technology of preparing.Object is by this technology of preparing, goes to solve the micro nano structure problem of tape surface.Thereby for super-hydrophobic, anti-icing field provides better base material.Traditional ice-covering-proof material has strict requirement to material itself.This technology is by simple experiment condition, and low cost and short period have been prepared the surface with micro nano structure at tape surface.This method is very low to requirement for experiment condition, and Repeatability reaches 100%.
The present invention is a kind of method of making the super-hydrophobic anti-ina thin film of micro nano structure at tape surface, it is characterized in that including the following step:
The first step, the preparation of padded coaming:
Graphite and zinc acetate solution are mixed, obtain mixed solution;
It is the drying box of 75 DEG C after 4 hours that mixed solution is placed in to temperature, then is placed in Muffle furnace 300～400 DEG C of high-temperature calcinations and is incubated 1 hour, after taking-up, is prepared into nanometer grade powder;
In described mixed solution, the mass ratio of graphite and zinc acetate is 3:1～10:1;
Second step, the modification of material surface:
First the PVDF of required growth ZnO is mixed with padded coaming, the PVDF that then surface has been obtained modifying spreads over tape surface, forms substrate combination material;
The mass ratio of described base material and padded coaming is 2:1～20:1;
The 3rd step, making ZnO array:
Substrate combination material is put in reactor, added and contain Zn
2+growth-promoting media, insulation reaction 10～12 hours under 85～90 DEG C of conditions.The cooling rear taking-up of question response still, substrate combination material surface covers with regular ZnO array, obtains the nanometer rods of the ZnO array arrangement of micron and nanometer composite structure;
The described Zn that contains
2+growth-promoting media be zinc nitrate or zinc acetate;
The 4th step, surface hydrophobicity processing:
The nanometer rods of the ZnO array arrangement of micron and nanometer composite structure is put into baking oven, under 30～60 DEG C of conditions, carry out drying and processing; Then transfer in vacuum drying chamber, drip in its vicinity two silicon fluorides.After vacuumizing 5～20min, move on in baking oven, under 60～90 DEG C of conditions, keep 3～6h, make and there is hydrophobic compound adhesive tape surface.
The film thickness of the nanometer rods of the ZnO array arrangement of micron and nanometer composite structure is 100～300 μ m, the nanostructured on ball surface, and nanometer rods is closely arranged in the surface of ball.
The contact angle that is bonded in the ZnO film of the micron and nanometer composite structure of tape surface is 155 °.
The invention has the advantages that:
1, the invention provides one simply, prepare micron and nanometer composite structure at tape surface cheaply, thereby play well super-hydrophobic and ice-covering-proof effect.For example, experiment is repeatability reliably, is just enough to illustrate the feasibility of this method.
2, the invention solves the combination problem of macromolecule and inorganic ZnO material.
3, the present invention can realize large area preparation and have the surface of micro nano structure, can realize large-scale production.
4, the present invention is loose to requirement for experiment condition, and running water can replace deionized water to complete experiment, for large-scale production provides condition.
5, manufacturing cycle of the present invention is short, can realize large-scale production.
Brief description of the drawings
Fig. 1 is the micron and nanometer composite structure SEM phenogram of tape surface.
Fig. 2 is the contact angle picture of film surface.
Fig. 3 has micro nano structure and only has the film of micrometer structure at delay and the deicing comparison diagram of freezing.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail.
The present invention is the nanometer rods of having prepared the ZnO array arrangement of micron and nanometer composite structure on the gluing of surfaces of adhesive tape, and concrete steps are:
The first step, the preparation of padded coaming:
Graphite and zinc acetate solution (concentration 0.1～3g/L) are mixed, obtain mixed solution; When mixing, ensure zinc acetate solution submergence graphitiferous material completely, can have zinc acetate at the adsorption that contains graphite material like this; After mixed solution is dry, is placed in interior 300～400 DEG C of high-temperature calcinations of Muffle furnace and is incubated 1 hour, after taking-up, being prepared into nanometer grade powder;
In described mixed solution, the mass ratio of graphite and zinc acetate is 3:1～10:1.
The described material that contains graphite first cleaned 1～5 hour with absolute ethyl alcohol before using.
In the present invention, the making of nanometer grade powder can be pulverized by ball mill.
Second step, the modification of material surface:
First the base material of required growth ZnO is mixed with padded coaming, substrate material surface has obtained modification, can adhere to one deck padded coaming at substrate material surface; Then the base material that surface has been obtained modifying spreads over tape surface, forms substrate combination material;
The mass ratio of described base material and padded coaming is 2:1～20:1;
Described base material is chosen macromolecule PVDF (Kynoar) micron ball;
The 3rd step, making ZnO array:
Substrate combination material is put in reactor, added and contain Zn
2+growth-promoting media, insulation reaction 10～12 hours under 85～90 DEG C of conditions.The cooling rear taking-up of question response still, substrate combination material surface covers with regular ZnO array, obtains the nanometer rods of the ZnO array arrangement of micron and nanometer composite structure.
The described Zn that contains
2+growth-promoting media be zinc nitrate or zinc acetate.
The 4th step, surface hydrophobicity processing:
The nanometer rods of the ZnO array arrangement of micron and nanometer composite structure is put into baking oven, under 30～60 DEG C of conditions, carry out drying and processing; Then transfer in vacuum drying chamber, drip in its vicinity two silicon fluorides.After vacuumizing 5～20min, move on in baking oven, under 60～90 DEG C of conditions, keep 3～6h, make and there is hydrophobic compound adhesive tape surface.
embodiment 1
The mass ratio of base material and padded coaming is the nanometer rods of the ZnO array arrangement of the micron and nanometer composite structure of 15:2, and concrete steps are:
The first step, the preparation of padded coaming:
Graphite and zinc acetate solution (concentration 0.2g/L) are mixed, obtain mixed solution; When mixing, ensure zinc acetate solution submergence graphitiferous material completely, can have zinc acetate at the adsorption that contains graphite material like this; After mixed solution is dry, is placed in the interior 400 DEG C of high-temperature calcinations of Muffle furnace and is incubated 1 hour, after taking-up, obtaining into nanometer grade powder through ball-milling treatment;
In described mixed solution, the mass ratio of graphite and zinc acetate is 5:1.
The described material that contains graphite first cleaned 3 hours with absolute ethyl alcohol before using;
In the present invention, the making of nanometer grade powder can provide by ball mill.
Ball milling condition: with the per minute 800 speed ball millings that turn, Ball-milling Time 15 hours.Ball-milling medium is that diameter is the agate ball of 2cm, and ratio of grinding media to material is 5:1.
Second step, the modification of material surface:
First PVDF (Kynoar) micron ball of required growth ZnO is mixed with padded coaming, PVDF (Kynoar) micron ball surface has obtained modification, can adhere to one deck padded coaming on PVDF (Kynoar) micron ball surface; Then PVDF (Kynoar) micron ball that surface has been obtained modifying spreads over tape surface, forms substrate combination material;
The 3rd step, making ZnO array:
Substrate combination material is put in reactor, added zinc nitrate, insulation reaction 10 hours under 90 DEG C of conditions.The cooling rear taking-up of question response still, substrate combination material surface covers with regular ZnO array, obtains the nanometer rods of the ZnO array arrangement of micron and nanometer composite structure.
Adopt the nanometer rods of the ZnO array arrangement of ESEM to the micron and nanometer composite structure making to carry out morphology analysis, the SEM phenogram of film surface shown in Figure 1.A is the large-area SEM figure of film surface, and b is side surface of thin film figure, and the thickness of film approximates 150 μ m, and c is the SEM figure of single PVDF ball, and d is the nanostructured on ball surface, and nanometer rods is closely arranged in the surface of ball.
The 4th step, surface hydrophobicity processing:
The nanometer rods of the ZnO array arrangement of micron and nanometer composite structure is put into baking oven, under 50 DEG C of conditions, carry out drying and processing; Then transfer in vacuum drying chamber, drip in its vicinity two silicon fluorides.After vacuumizing 10min, move on in baking oven, under 60 DEG C of conditions, keep 4h, make and there is hydrophobic compound adhesive tape surface.
Adopt contact angle measurement (containing cold) to measure thering is hydrophobic compound adhesive tape surface: shown in Figure 2, the compound adhesive tape surface of preparation has extraordinary gas-solid ratio, contact angle is 155 °, can play well super-hydrophobic, can be laid in need hydrophobic anti-icing substrate surface.On cold platform, freeze and postpone and deicing test, the anti-icing and deicing comparison diagram of film shown in Figure 3.(a) for having the icing delay of micron and nanometer composite structure film, under-10 DEG C of conditions, after 6850s, drop freezes, and the size of drop is 6 μ L.In freeze-melting process, there is not significant change in the border of drop.(b) for only having the icing delay experiment of micron ball structural membrane, under similarity condition, drop is sprawled at 450s, and freezes in the time of 500s.After freezing-melting, sprawl on the border of drop, and can not return to original state.(c) be the ice detachment with micron and nanometer composite structure film 2h under-15 DEG C of conditions.Drop is spherical in shape on its surface, and contact area is very little, so just departed from surface when film departs from cold, has good deicing effect.(d) be the ice detachment of only having 2h under DEG C condition of micron ball body structure surface-15.Because drop is sprawled before freezing, so very large with the real contact area of film after freezing, this has just increased the difficulty of deicing, thus film in cold process of disengaging, there is not break-off in ice.
embodiment 2
The mass ratio of base material and padded coaming is the nanometer rods of the ZnO array arrangement of the micron and nanometer composite structure of 5:1, and concrete steps are:
The first step, the preparation of padded coaming:
Graphite and zinc acetate solution (concentration 1g/L) are mixed, obtain mixed solution; When mixing, ensure zinc acetate solution submergence graphitiferous material completely, can have zinc acetate at the adsorption that contains graphite material like this; After mixed solution is dry, is placed in the interior 300 DEG C of high-temperature calcinations of Muffle furnace and is incubated 1 hour, after taking-up, obtaining into nanometer grade powder through ball-milling treatment;
In described mixed solution, the mass ratio of graphite and zinc acetate is 3:1.
The described material that contains graphite first cleaned 2.5 hours with absolute ethyl alcohol before using;
In the present invention, the making of nanometer grade powder can provide by ball mill.Ball milling condition: with the per minute 800 speed ball millings that turn, Ball-milling Time 15 hours.Ball-milling medium is that diameter is the agate ball of 2cm, and ratio of grinding media to material is 5:1.
Second step, the modification of material surface:
First PVDF (Kynoar) micron ball of required growth ZnO is mixed with padded coaming, PVDF (Kynoar) micron ball surface has obtained modification, can adhere to one deck padded coaming on PVDF (Kynoar) micron ball surface; Then PVDF (Kynoar) micron ball that surface has been obtained modifying spreads over tape surface, forms substrate combination material;
The 3rd step, making ZnO array:
Substrate combination material is put in reactor, added zinc nitrate, insulation reaction 12 hours under 80 DEG C of conditions.The cooling rear taking-up of question response still, substrate combination material surface covers with regular ZnO array, obtains the nanometer rods of the ZnO array arrangement of micron and nanometer composite structure.
Through the morphology analysis of ESEM, the thickness of film equals 100 μ m, and c is the SEM figure of single PVDF ball, and d is the nanostructured on ball surface, and nanometer rods is closely arranged in the surface of ball.
The 4th step, surface hydrophobicity processing:
The nanometer rods of the ZnO array arrangement of micron and nanometer composite structure is put into baking oven, under 50 DEG C of conditions, carry out drying and processing; Then transfer in vacuum drying chamber, drip in its vicinity two silicon fluorides.After vacuumizing 10min, move on in baking oven, under 60 DEG C of conditions, keep 4h, make and there is hydrophobic compound adhesive tape surface.
Measure thering is hydrophobic compound adhesive tape surface through contact angle measurement (containing cold): the compound adhesive tape surface of preparation has extraordinary gas-solid ratio, contact angle is 155 °, can play well super-hydrophobic, can be laid in need hydrophobic anti-icing substrate surface.On cold platform, freeze and postpone and deicing test, drop is spherical in shape on its surface, and contact area is very little, so just departed from surface when film departs from cold, has good deicing effect.Only has the ice detachment of micron ball body structure surface.Because drop is sprawled before freezing, so very large with the real contact area of film after freezing, this has just increased the difficulty of deicing, thus film in cold process of disengaging, there is not break-off in ice.
embodiment 3
The mass ratio of base material and padded coaming is the nanometer rods of the ZnO array arrangement of the micron and nanometer composite structure of 10:1, and concrete steps are:
The first step, the preparation of padded coaming:
Graphite and zinc acetate solution (concentration 0.8g/L) are mixed, obtain mixed solution; When mixing, ensure zinc acetate solution submergence graphitiferous material completely, can have zinc acetate at the adsorption that contains graphite material like this; After mixed solution is dry, is placed in the interior 350 DEG C of high-temperature calcinations of Muffle furnace and is incubated 1 hour, after taking-up, obtaining into nanometer grade powder through ball-milling treatment;
In described mixed solution, the mass ratio of graphite and zinc acetate is 2:1.
The described material that contains graphite first cleaned 3 hours with absolute ethyl alcohol before using;
In the present invention, the making of nanometer grade powder can provide by ball mill.Ball milling condition: with the per minute 800 speed ball millings that turn, Ball-milling Time 15 hours.Ball-milling medium is that diameter is the agate ball of 2cm, and ratio of grinding media to material is 5:1.
Second step, the modification of material surface:
First PVDF (Kynoar) micron ball of required growth ZnO is mixed with padded coaming, PVDF (Kynoar) micron ball surface has obtained modification, can adhere to one deck padded coaming on PVDF (Kynoar) micron ball surface; Then PVDF (Kynoar) micron ball that surface has been obtained modifying spreads over tape surface, forms substrate combination material;
The 3rd step, making ZnO array:
Substrate combination material is put in reactor, added zinc nitrate, insulation reaction 12 hours under 85 DEG C of conditions.The cooling rear taking-up of question response still, substrate combination material surface covers with regular ZnO array, obtains the nanometer rods of the ZnO array arrangement of micron and nanometer composite structure.
The nanometer rods of the ZnO array arrangement through ESEM to the micron and nanometer composite structure making is carried out morphology analysis, and the thickness of film equals 160 μ m, the nanostructured on ball surface, and nanometer rods is closely arranged in the surface of ball.
The 4th step, surface hydrophobicity processing:
The nanometer rods of the ZnO array arrangement of micron and nanometer composite structure is put into baking oven, under 35 DEG C of conditions, carry out drying and processing; Then transfer in vacuum drying chamber, drip in its vicinity two silicon fluorides.After vacuumizing 15min, move on in baking oven, under 80 DEG C of conditions, keep 3h, make and there is hydrophobic compound adhesive tape surface.
Measure thering is hydrophobic compound adhesive tape surface through contact angle measurement (containing cold): the compound adhesive tape surface of preparation has extraordinary gas-solid ratio, contact angle is 155 °, can play well super-hydrophobic, can be laid in need hydrophobic anti-icing substrate surface.On cold platform, freeze and postpone and deicing test, drop is spherical in shape on its surface, and contact area is very little, so just departed from surface when film departs from cold, has good deicing effect.Only has the ice detachment of micron ball body structure surface.Because drop is sprawled before freezing, so very large with the real contact area of film after freezing, this has just increased the difficulty of deicing, thus film in cold process of disengaging, there is not break-off in ice.
Claims (5)
1. a method of making the super-hydrophobic anti-ina thin film of micro nano structure at tape surface, is characterized in that including the following step:
The first step, the preparation of padded coaming:
Graphite and zinc acetate solution are mixed, obtain mixed solution;
It is the drying box of 75 DEG C after 4 hours that mixed solution is placed in to temperature, then is placed in Muffle furnace 300～400 DEG C of high-temperature calcinations and is incubated 1 hour, after taking-up, is prepared into nanometer grade powder;
In described mixed solution, the mass ratio of graphite and zinc acetate is 3:1～10:1;
Second step, the modification of material surface:
First the PVDF of required growth ZnO is mixed with padded coaming, the PVDF that then surface has been obtained modifying spreads over tape surface, forms substrate combination material;
The mass ratio of described base material and padded coaming is 2:1～20:1;
The 3rd step, making ZnO array:
Substrate combination material is put in reactor, added and contain Zn
2+growth-promoting media, insulation reaction 10～12 hours under 85～90 DEG C of conditions.The cooling rear taking-up of question response still, substrate combination material surface covers with regular ZnO array, obtains the nanometer rods of the ZnO array arrangement of micron and nanometer composite structure;
The described Zn that contains
2+growth-promoting media be zinc nitrate or zinc acetate;
The 4th step, surface hydrophobicity processing:
The nanometer rods of the ZnO array arrangement of micron and nanometer composite structure is put into baking oven, under 30～60 DEG C of conditions, carry out drying and processing; Then transfer in vacuum drying chamber, drip in its vicinity two silicon fluorides.After vacuumizing 5～20min, move on in baking oven, under 60～90 DEG C of conditions, keep 3～6h, make and there is hydrophobic compound adhesive tape surface.
2. the method for super-hydrophobic anti-ina thin film of making micro nano structure at tape surface according to claim 1, is characterized in that: described in contain graphite material before using, first clean 1～5 hour with absolute ethyl alcohol.
3. the method for super-hydrophobic anti-ina thin film of making micro nano structure at tape surface according to claim 1, is characterized in that: to the graphite after high-temperature calcination with the per minute 800 speed ball millings that turn, Ball-milling Time 15 hours; Ball-milling medium is that diameter is the agate ball of 2cm, and ratio of grinding media to material is 5:1; Ball milling obtains nanometer grade powder.
4. method of making the super-hydrophobic anti-ina thin film of micro nano structure at tape surface according to claim 1, is characterized in that: the contact angle on compound adhesive tape surface is 155 °.
5. method of making the super-hydrophobic anti-ina thin film of micro nano structure at tape surface according to claim 1, it is characterized in that: the film thickness of the nanometer rods of the ZnO array arrangement of micron and nanometer composite structure is 100～300 μ m, the nanostructured on ball surface, nanometer rods is closely arranged in the surface of ball.
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| CN201410337118.3A CN104085853A (en) | 2014-07-15 | 2014-07-15 | Method for manufacturing micro-nanometer structure super-hydrophobic anti-icing thin film on surface of adhesive tape |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104674197A (en) * | 2015-01-31 | 2015-06-03 | 南昌航空大学 | Method for preparing ice-coating resistant zinc oxide coating on copper surface |
| CN110132668A (en) * | 2019-04-28 | 2019-08-16 | 西安培华学院 | A kind of super-hydrophobic processing method of conventional slide |
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| CN103205211A (en) * | 2013-04-11 | 2013-07-17 | 浙江理工大学 | Preparation method of super-hydrophobic adhesive tape |
| CN103408060A (en) * | 2013-07-23 | 2013-11-27 | 北京航空航天大学 | Method of preparing ZnO array on multi-structure polymer surface |
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2014
- 2014-07-15 CN CN201410337118.3A patent/CN104085853A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205211A (en) * | 2013-04-11 | 2013-07-17 | 浙江理工大学 | Preparation method of super-hydrophobic adhesive tape |
| CN103408060A (en) * | 2013-07-23 | 2013-11-27 | 北京航空航天大学 | Method of preparing ZnO array on multi-structure polymer surface |
Non-Patent Citations (1)
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| MENGXI WEN ET AL.: "Antifogging and Icing-Delay Properties of Composite Micro- and Nanostructured Surfaces", 《APPLIED MATERIALS & INTERFACES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104674197A (en) * | 2015-01-31 | 2015-06-03 | 南昌航空大学 | Method for preparing ice-coating resistant zinc oxide coating on copper surface |
| CN104674197B (en) * | 2015-01-31 | 2017-02-22 | 南昌航空大学 | Method for preparing ice-coating resistant zinc oxide coating on copper surface |
| CN110132668A (en) * | 2019-04-28 | 2019-08-16 | 西安培华学院 | A kind of super-hydrophobic processing method of conventional slide |
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Application publication date: 20141008 |