CN109402570A - Metal protection system based on nano-array - Google Patents
Metal protection system based on nano-array Download PDFInfo
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- CN109402570A CN109402570A CN201811520259.3A CN201811520259A CN109402570A CN 109402570 A CN109402570 A CN 109402570A CN 201811520259 A CN201811520259 A CN 201811520259A CN 109402570 A CN109402570 A CN 109402570A
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
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Abstract
The metal protection system based on nano-array that this application involves a kind of, the metal protection system include metallic substrates, the micro-nano structure layer in metallic substrates and the surface covering being applied on the micro-nano structure layer；The micro-nano structure layer includes zinc membrane array and nano-titanium dioxide film, zinc membrane array is to be prepared by ultraviolet photolithographic combination magnetron sputtering method, it is made of the dot matrix of micro-meter scale, nano-titanium dioxide film is prepared by electrodeposition process, and coat zinc membrane array, which also shows as a kind of array of protrusions of micro-meter scale.
Description
Technical field
This application involves metal protection field more particularly to a kind of metal protection systems based on nano-array.
Background technique
In production and living, the metal of everyday exposure, other than a small amount of inert metal, most metals and its alloy are certainly
The problem of corrosion can be all faced under right environment.Corrosion of metal causes the serious waste of resource and the energy, serious person, metal corruption
Erosion can also threaten the life security of people, after metal is corroded, in the case where shape, color and mechanical properties can occur
How drop, to be easy to cause the accidents such as damage of facilities, pipe leakage, contamination of products, therefore, slow down or prevent the corruption of metal
Erosion is significant.For the means of defence of metal erosion, element doping method, electrochemical process, coating etc. common are；Coating
Method is one layer of protective layer to be formed in metal surface, by the physical methods such as brushing, spraying for separating corrosive media and metal
Substrate, to reach protection purpose, this method preparation process is simple, cost of material is low, good corrosion resistance, be it is a kind of application compared with
Extensive metal erosion means of defence, coating antiseptic erosion application is one of widest anti-corrosion means.Coating is used to metal
It is protected, coating can be used as physical barriers, penetrate into metal watch to stop or slow down water, oxygen and corrosive ion
Face, in general, coating include pretreatment layer and surface covering, the pretreatment layer among metal coating system, effect
It is to carry out good combination with metallic substrates, prevents coating foaming, removes or fall off, it is good to the binding force of entire coating system
It is bad, it plays a crucial role；Further, since causing local corrosion fast after the intrinsic porosity and coating damage of metal coating
Degree is accelerated to be also one of the focal issue for influencing coating antiseptic ability.
Summary of the invention
For realistic problem set forth above, the application in conjunction with micro-nano structure, proposes metal coating based on nanometer
The metal protection system of array, the metal protection system construct a kind of middle layer with super-hydrophobicity based on micro-nano structure,
It is good with substrate caking power, and effectively reduces porosity intrinsic in coating.
The metal protection system based on nano-array is provided in the embodiment of the present invention, which includes gold
Belong to substrate, the micro-nano structure layer in metallic substrates and the surface covering being applied on the micro-nano structure layer；The micro-nano structure layer
Including zinc membrane array and nano-titanium dioxide film, zinc membrane array is to be prepared by ultraviolet photolithographic combination magnetron sputtering method, by micro-
The dot matrix of metrical scale is constituted, and nano-titanium dioxide film is prepared by electrodeposition process, and zinc membrane array is coated, the nano-silica
Change the array of protrusions that titanium film also shows as a kind of micro-meter scale；The surface covering is a kind of low-surface energy substance.
The technical solution that the embodiment of the present invention provides can include the following benefits:
Metal protection system of the invention includes metallic substrates, micro-nano structure layer and surface covering, the micro-nano structure layer by
Zinc membrane array and nano-titanium dioxide film are constituted, and show as a kind of super-drainage structure, have good corrosion resistance, this
Outside, zinc membrane array and nano-titanium dioxide and metallic substrates binding force are strong, lead between zinc membrane array and nano-titanium dioxide film
Zinc peroxide nano wire enhances binding force and reduces the hole in nano-titanium dioxide film so that the protection system is not easily to fall off
Gap rate, protective capacities are strong.
The additional aspect of the application and advantage will be set forth in part in the description, and will partially become from the following description
It obtains obviously, or recognized by the practice of the application.It should be understood that above general description and following detailed description are only
Be it is exemplary and explanatory, the application can not be limited.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawings, but the embodiment in attached drawing is not constituted to any limit of the invention
System, for those of ordinary skill in the art, without creative efforts, can also obtain according to the following drawings
Other attached drawings.
Fig. 1 is the making step schematic diagram of micro-nano structure layer in metal protection system of the present invention.
Specific embodiment
Example embodiments are described in detail here, and the example is illustrated in the accompanying drawings.Following description is related to
When attached drawing, unless otherwise indicated, the same numbers in different drawings indicate the same or similar elements.Following exemplary embodiment
Described in embodiment do not represent all embodiments consistented with the present invention.On the contrary, they be only with it is such as appended
The example of device and method being described in detail in claims, some aspects of the invention are consistent.
Embodiments herein is related to a kind of metal protection system based on nano-array, which includes gold
Belong to substrate 1, the micro-nano structure layer in metallic substrates 1 and the surface covering being applied on the micro-nano structure layer.
The metallic substrates 1 are preferably stainless steel base, before constructively stating metal protection system, it is necessary first to stainless
Handled to base steel.
Treatment process are as follows: by stainless steel base after No. 14 abrasive paper for metallograph mechanical grindings, be then placed in 80 DEG C of oil removing
Oil removing 5min in liquid, then the ultrasound 20min at 50 DEG C, after finally successively being cleaned with acetone, ethyl alcohol, deionized water, fast heated-air
Drying, places 20h in drying box.
Wherein, the composition of above-mentioned degreasing fluid are as follows: sodium carbonate 8g/L, sodium metasilicate 5g/L, sodium polyphosphate 8g/L, dodecyl
Sodium sulfonate 1g/L, alkyl phenol polyoxyethylene ether 5mL/L.
After above-mentioned metallic substrates 1 are processed, then micro-nano structure layer is prepared in metallic substrates 1.
In conjunction with Fig. 1, which includes successively in the zinc membrane array 2 and nanometer titanium dioxide of metal substrate surface setting
Titanium film 3, nano-titanium dioxide film 3 are set to 2 surface of zinc membrane array, the shape of the specific micro-nano structure layer as shown in Figure 1
At process.
In above-mentioned micro-nano structure layer, which is a kind of array of micro-meter scale, is prepared by Ultraviolet lithography,
The coarse structure of the first bicron scale is formed on 1 surface of metallic substrates using the zinc membrane array 2, then in the zinc membrane array 2
On the basis of prepare nano-titanium dioxide film 3, and zinc membrane array 2 is coated.
On the one hand, which is coated on 2 surface of zinc membrane array, utilizes the micro- of above-mentioned zinc membrane array 2
Metrical scale, the nano-titanium dioxide film 3 can also show as a kind of array of protrusions of micro-meter scale；Then on the other hand,
The nano-titanium dioxide film 3 is prepared using electrodeposition process, which has the thick of micro/nano-scale
Rough, porous structure；To, in conjunction with nano-titanium dioxide film 3 array of protrusions and and its rough porous structure on surface formed
A kind of super-drainage structure of multidimensional, which is to have one of necessary condition of hydrophobic performance, can be completely cut off
The contact with metallic substrates such as steam, plays the role of protection.
In addition, in terms of with the binding force of metallic substrates 1: zinc membrane array 2 is by magnetron sputtering apparatus, with Metal Substrate
Bottom 1 is tightly combined；Nano-titanium dioxide film 3 is electro-deposition preparation, strong with metallic substrates 1 or 2 binding force of zinc membrane array,
Not easily to fall off, protection is played the role of in the contact with metallic substrates such as energy starvation, corrosive liquids.
In being preferably carried out mode, the length and width high yardstick of single dot matrix is 30 × 15 × 1 μm in the zinc membrane array 2, often
Above and below between a dot matrix, between left and right every respectively 80 μm, 50 μm.
In being preferably carried out mode, the nano-titanium dioxide film 3 with a thickness of 5 μm.
After preparing micro-nano structure in metallic substrates 1, then in metallic substrates 1 prepare surface covering.The surface covering is set
It is a kind of low-surface energy substance on nano-titanium dioxide film, with the array of protrusions of nano-titanium dioxide film, coarse
Porous structure together forms super-hydrophobic two necessary conditions --- higher surface roughness and low-surface energy substance, thus
A kind of super hydrophobic surface is constructed.
In another preferred embodiment, which, which also grows, zinc oxide nanowire, the zinc oxide nano
The length of rice noodles is 3~5 μm.Zinc oxide nanowire has excellent semiconducting behavior, is generally used for Flied emission, gas sensing
The fields such as device, and in the application, one is constructed using zinc oxide nanowire and the nano-titanium dioxide film with porous structure
The compact micro-nano structure layer of kind, reduces the porosity of micro-nano structure layer, substantially increases anticorrosion ability.In zinc film battle array
List is looked unfamiliar with after nano wire, then electro-deposition nano-titanium dioxide film on this basis, which will
Nano wire cladding, since nano wire specific surface area is larger, increases the binding force with nano-titanium dioxide film, to mention significantly
The high binding force of nano-titanium dioxide film and metallic substrates, so that the metal protection system is not easily to fall off, binding force is strong.
Embodiment 1
In this embodiment, the preparation process of metal protection system described in technical scheme are as follows:
Step 1, metallic substrates are handled: by metallic substrates after No. 14 abrasive paper for metallograph mechanical grindings, being put into 80 DEG C and removes
Oil removing 5min in oil liquid, then in 50 DEG C of ultrasound 20min, after finally successively being cleaned with acetone, ethyl alcohol, deionized water, fast heated-air
Drying, places 20h in drying box, spare；
Step 2, micro-nano structure layer is prepared:
1) zinc membrane array is deposited:
A layer photoresist is coated in metal substrate surface, then drying utilizes magnetron sputtering technique through overexposure, development,
One layer of zinc film is deposited in photoresist surface after development, and zinc film thickness is 500nm, is then washed off photoresist using acetone, this
Sample forms zinc membrane array in metal substrate surface；
2) TiO 2 precursor solution is configured:
By 12.5ml dehydrated alcohol, 0.5ml deionized water and 0.25ml mixed in hydrochloric acid, then by mixed liquor stirring feelings
It is slowly added under condition in the mixed liquor of 10ml butyl titanate and 12.5ml dehydrated alcohol, stirs 30min, ultrasonic 15min is obtained
To TiO 2 precursor solution；
3) nano-titanium dioxide film is prepared:
TiO 2 precursor solution obtained above is added in three slot electrodes, by the above-mentioned zinc membrane array that is deposited with
Metallic substrates are used as reference electrode, platinum to electrode as working electrode, Ag/AgCl, and controlling potential is in -1.3V, deposition
Between be 300s, after being rinsed with deionized water 50 DEG C drying, obtain nano-titanium dioxide film；
Step 3, surface covering is prepared
The metallic substrates obtained above for being covered with micro-nano structure layer are put into the 17 fluorine last of the ten Heavenly stems rouge trimethyl-tryptophanes of 1ml
In the toluene solution (5v%) of silane, sealing keeps the temperature 5h in 80 DEG C of baking ovens, completes the modification of low-surface energy substance.
In the present embodiment, which shows the more of micro/nano-scale after above-mentioned micro-nano structure layer preparation
Porous, and, the array of protrusions structure with micro-meter scale is coated with low-surface energy substance on this basis, and hydrophobicity is good,
Compactness is good.
The protective performance of the metal protection system is showed by hydrophobicity and corrosion resistance；
For hydrophobicity, when nano-titanium dioxide film sedimentation time difference, different contact angles is shown as, it is as follows
Table:
| Sedimentation time/s | Contact angle/degree |
| 0 | 124 |
| 50 | 135 |
| 100 | 143 |
| 150 | 149 |
| 200 | 151 |
| 250 | 154 |
| 300 | 159 |
| 350 | 159 |
| 400 | 157 |
| 500 | 152 |
When sedimentation time is 300~400s, Maximum Contact angle is 159 degree, shows good hydrophobicity, so as to
Effectively contact of the isolation steam with metallic substrates, and also there is good self-cleaning performance.
For electro-chemical test, which is put into sodium chloride solution, is placed for 24 hours, the opposite change of contact angle
Change less than 10%, shows good Corrosion Protection, protective capacities is strong.
Embodiment 2
Specific steps such as embodiment 1, difference is, after depositing zinc membrane array, before preparing nano-titanium dioxide film,
Using CVD method in zinc membrane array surface growth of zinc oxide nano line:
The step of growth of zinc oxide nano line are as follows:
The metallic substrates are put into tube furnace, 800 DEG C, in temperature-rise period are warming up in 2h, are passed through argon gas as guarantor
Gas is protected, then keeps the temperature 5h at 800 DEG C, in insulating process, is passed through hydrogen as reducing gas, then by tube furnace nature
Cooling, on zinc membrane array surface, growth has zinc oxide nanowire, which is 3~5 μm, diameter 200nm.
The metallic substrates show the porous property of micro/nano-scale after the preparation of the micro-nano structure layer of above-described embodiment,
And the array of protrusions structure with micro-meter scale, it is coated with low-surface energy substance on this basis, hydrophobicity is good, compactness
It is good.
The protective performance of the metal protection system is showed by hydrophobicity and corrosion resistance；
For hydrophobicity, when nano-titanium dioxide film sedimentation time difference, different contact angles is shown as, it is as follows
Table:
| Sedimentation time/s | Contact angle/degree |
| 0 | 123 |
| 50 | 137 |
| 100 | 140 |
| 150 | 147 |
| 200 | 153 |
| 250 | 154 |
| 300 | 159 |
| 350 | 163 |
| 400 | 165 |
| 500 | 163 |
When sedimentation time is 350~400s, Maximum Contact angle is 165 degree, shows good hydrophobicity, compares implementation
Example 1, Maximum Contact angle increase, and so as to effectively completely cut off contact of the steam with metallic substrates, and also have good from clear
Clean performance.
For electro-chemical test, which is put into sodium chloride solution, is placed for 24 hours, the opposite change of contact angle
Change less than 10%, shows good Corrosion Protection, protective capacities is strong.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of metal protection system based on nano-array, which is characterized in that the metal protection system includes metallic substrates, sets
In the micro-nano structure layer in metallic substrates and the surface covering being applied on the micro-nano structure layer；The micro-nano structure layer includes zinc film battle array
Column and nano-titanium dioxide film, zinc membrane array is to be prepared by ultraviolet photolithographic combination magnetron sputtering method, by the point of micro-meter scale
Battle array is constituted, and nano-titanium dioxide film is prepared by electrodeposition process, and zinc membrane array is coated, the nano-titanium dioxide film
Show as a kind of array of protrusions of micro-meter scale；The surface covering is a kind of low-surface energy substance.
2. metal protection system according to claim 1, which is characterized in that the length, width and height of single dot matrix in the zinc membrane array
Scale is 30 × 15 × 1 μm.
3. metal protection system according to claim 2, which is characterized in that in the zinc membrane array between dot matrix up and down,
Between left and right every respectively 80 μm, 50 μm.
4. metal protection system according to claim 3, which is characterized in that the nano-titanium dioxide film with a thickness of 5 μ
m。
5. metal protection system according to claim 4, which is characterized in that
The preparation process of the metal protection system are as follows:
Step 1, metallic substrates are handled: by metallic substrates after No. 14 abrasive paper for metallograph mechanical grindings, being put into 80 DEG C of degreasing fluid
Middle oil removing 5min, then in 50 DEG C of ultrasound 20min, after finally successively being cleaned with acetone, ethyl alcohol, deionized water, fast heated-air drying,
20h is placed in drying box, it is spare；
Step 2, micro-nano structure layer is prepared:
1) zinc membrane array is deposited:
A layer photoresist is coated in metal substrate surface, then drying utilizes magnetron sputtering technique through overexposure, development, aobvious
One layer of zinc film is deposited in the photoresist surface of movie queen, and zinc film thickness is 500nm, then washes off photoresist using acetone, exists in this way
Metal substrate surface forms zinc membrane array；
2) TiO 2 precursor solution is configured:
By 12.5ml dehydrated alcohol, 0.5ml deionized water and 0.25ml mixed in hydrochloric acid, then in the case of stirring by mixed liquor
It is slowly added into the mixed liquor of 10ml butyl titanate and 12.5ml dehydrated alcohol, stirs 30min, ultrasonic 15min obtains two
Titania precursor liquid solution；
3) nano-titanium dioxide film is prepared:
TiO 2 precursor solution obtained above is added in three slot electrodes, by the above-mentioned metal for being deposited with zinc membrane array
Substrate is used as reference electrode, platinum to electrode as working electrode, Ag/AgCl, and controlling potential is in -1.3V, sedimentation time
300s, 50 DEG C of drying, obtain nano-titanium dioxide film after being rinsed with deionized water；
Step 3, surface covering is prepared
The metallic substrates obtained above for being covered with micro-nano structure layer are put into the 17 fluorine last of the ten Heavenly stems rouge trimethyl-tryptophane silane of 1ml
Toluene solution (5v%) in, sealing, keep the temperature 5h in 80 DEG C of baking ovens, complete the modification of low-surface energy substance.
6. metal protection system according to claim 1, which is characterized in that in the micro-nano structure layer, in zinc film spot battle array
It is equipped with zinc oxide nanowire, nano-titanium dioxide film coats zinc membrane array, zinc oxide nanowire, and nano-titanium dioxide is thin
Film also shows as a kind of array of protrusions of micro-meter scale.
7. metal protection system according to claim 6, which is characterized in that the length of the zinc oxide nanowire is 3~5 μ
m。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100116669A1 (en) * | 2005-01-06 | 2010-05-13 | The Boeing Company | Self-cleaning superhydrophobic surface |
| CN102011153A (en) * | 2010-12-24 | 2011-04-13 | 上海交通大学 | Preparation method of metal-base superhydrophobic material |
| CN106929811A (en) * | 2017-03-31 | 2017-07-07 | 深圳智达机械技术有限公司 | A kind of metal protection system based on micro-nano structure |
| CN106973135A (en) * | 2017-03-31 | 2017-07-21 | 上海琛岫自控科技有限公司 | A kind of surface electro-deposition SiO2Smart mobile phone shell |
| CN107675223A (en) * | 2017-09-19 | 2018-02-09 | 南京理工大学 | The method that petal-shaped zinc super hydrophobic surface is prepared using plant leaf blade template |
-
2018
- 2018-12-12 CN CN201811520259.3A patent/CN109402570A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100116669A1 (en) * | 2005-01-06 | 2010-05-13 | The Boeing Company | Self-cleaning superhydrophobic surface |
| CN102011153A (en) * | 2010-12-24 | 2011-04-13 | 上海交通大学 | Preparation method of metal-base superhydrophobic material |
| CN106929811A (en) * | 2017-03-31 | 2017-07-07 | 深圳智达机械技术有限公司 | A kind of metal protection system based on micro-nano structure |
| CN106973135A (en) * | 2017-03-31 | 2017-07-21 | 上海琛岫自控科技有限公司 | A kind of surface electro-deposition SiO2Smart mobile phone shell |
| CN107675223A (en) * | 2017-09-19 | 2018-02-09 | 南京理工大学 | The method that petal-shaped zinc super hydrophobic surface is prepared using plant leaf blade template |
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