CN107675223A - The method that petal-shaped zinc super hydrophobic surface is prepared using plant leaf blade template - Google Patents
The method that petal-shaped zinc super hydrophobic surface is prepared using plant leaf blade template Download PDFInfo
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- CN107675223A CN107675223A CN201710847729.6A CN201710847729A CN107675223A CN 107675223 A CN107675223 A CN 107675223A CN 201710847729 A CN201710847729 A CN 201710847729A CN 107675223 A CN107675223 A CN 107675223A
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- zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
Abstract
The invention discloses a kind of method that petal-shaped zinc super hydrophobic surface is prepared using plant leaf blade template.This method first passes through nonoxidizing atmosphere sintering, obtains the carbon materials with blade construction using super-hydrophobicity plant leaf blade as template；Petal-shaped zinc surface is obtained in carbon materials electroplating surface a thin layer zinc by electric plating method again；Zinc surface after silicon fluoride is modified, has ultra-hydrophobicity again, obtains petal-shaped zinc super hydrophobic surface.Zinc surface made from the inventive method had both remained the mastoid process structure of blade surface, petal-shaped flake structure in mastoid process is remained again, high level is used for reference naturally, this hierarchy causes zinc surface to have excellent ultra-hydrophobicity, improves waterproof absorption and the antiseptic power of zinc.
Description
Technical field
The invention belongs to technical field of material, is related to a kind of method for preparing petal-shaped zinc super hydrophobic surface, specifically
It is related to a kind of method for preparing petal-shaped zinc super hydrophobic surface using plant leaf blade template and plating.
Background technology
Zinc and its alloy are a kind of widely used non-ferrous metals of the mankind, and its calenderability, wearability, castability are good.Meanwhile
One layer of uniform fine and closely woven oxide film protection layer can be formed after being aoxidized due to zinc alloy surface, therefore zinc has excellent anti-air rotten
Corrosion energy.At present, the zinc of more than half is used for zinc-plated, i.e., one layer of zinc is plated on the surface of metal, alloy or other materials to rise
To corrosion-resisting function, zinc is then widely used in the industries such as automobile, building, ship, light industry.But under moist and sour environment
The zinc coating used, zinc easily adsorb acid water because surface energy is higher, and this can cause the heavy corrosion of zinc coat, serious shadow
The attractive in appearance of galvanizing production has been rung, and has influenceed properties of product, the steady operation to product and equipment brings larger harm.Even if
Moist storage rust staining is formed in use, zinc surface is also easily stained with steam under neutral moist environment, after a period of time, this
It has impact on the attractive in appearance of product.Although different environment is different to the extent of corrosion of zinc, the corrosion of the presence of water to zinc serves
Crucial damaging effect.Super hydrophobic surface is made on Zinc material can efficiently solve these problems, super-hydrophobic zinc surface
The attachment of water can be effectively reduced, so as to avoid corrosion caused by water so that its product aesthetic property and performance are increased dramatically.
At present, super-hydrophobic zinc surface mainly passes through artificial method construct coarse structure, such as the immersion of electrolysis, solution
The methods of method, electrochemical etching method, chemical replacement deposition method, sol-gal process, hydro-thermal method, then with the thing with low-surface-energy
Matter carries out surface modification and super hydrophobic material is made.Ma Fumin et al. uses solution infusion method, and zinc metal sheet is immersed in into hydrochloric acid and bay
In the ethanol solution of acid, the bar-shaped and structure of sheet is obtained on zinc metal sheet surface, obtained zinc surface contact angle is up to 154 °, is dredged
Water performance is general（Ma Fumin etc., a step infusion method prepare the super-hydrophobic zinc surface of micrometer structure, Midwest in 2013
Area's inorganic chemistry chemical industry science conference Papers collection, 2013,45-47）.Zhang Wanqiang et al. uses chemical replacement deposition method, will
Zinc metal sheet is put into copper-bath and enters line replacement reaction, and nano copper particle, obtained zinc surface contact angle highest are formed in zinc surface
For 155 °, hydrophobic performance performance is also general（Zhang Wanqiang etc., displacement reaction prepare zinc surface based superhydrophobic thin films, Chemical Industry in Guangzhou,
2015, 43(11), 72–74）.There is the coarse structure degree of roughness that the reason for these are insufficient essentially consists in these manual constructions
Not enough.Obtain relatively good hydrophobic material key and be the multistage complicated nano-micro structure of structured surface.Some of nature
Plant forms micro-nano hierarchy during long-term evolution, and the structure makes plant possess ultra-hydrophobicity, as lotus leaf,
Rice-pudding leaf, Rice Leaf etc..At present, researcher is template just using plant structure, is prepared by physicochemical method with plant
The super hydrophobic surface of thing structure, these surface exhibits go out excellent hydrophobic performance.Chang Li waits people quietly using palm leaf as template, passes through leaching
The method of stain sintering prepares super-hydrophobic copper surface.But these plant leaf blade templates can lose a part in sintering process
Fine structure, such as palm leaf, the nanoscale petal-shaped thin slice on its surface has not just existed after vacuum-sintering, to a certain extent
It has lost the structure multistage complexity of original template（L.J. Chang, et al., Biomimetic fabrication of
indicalamus-leaf-like structured copper surface with superhydrophobic
properties, Materials Transactions, 2013, 52(12), 1345-9678）.Chen Kai et al. passes through plating
Method on lotus leaf carbon be made super-hydrophobic copper surface, although copper forms more tiny graininess knot in micron order mastoid process
Structure, but differed greatly with petal-like structures, fail the natural structure for ideally retaining blade（K. Chen, et al.,
Preparation of a Cu surface with the hierarchical structure of a lotus leaf
via electroplating and its superhydrophobicity, Materials Transactions, 2017,
3, 58(8), 1231-1234）.
The content of the invention
It is an object of the invention to provide a kind of method that petal-shaped zinc super hydrophobic surface is prepared using plant leaf blade template.
The technical solution for realizing the object of the invention is：
A kind of method that petal-shaped zinc super hydrophobic surface is prepared using plant leaf blade template, with naturally, super using rice-pudding leaf, lotus leaf etc.
Hydrophobic plant blade protects the method for sintering to obtain the carbon that the blade of high-fidelity constructs as template by nonoxidizing atmosphere
Cellulosic material, re-plating obtains one layer of petal-shaped zinc film on its surface, and is modified with low-surface energy substance, and it is super-hydrophobic that zinc is made
Surface.
Comprise the following steps that：
Step 1, dry super-hydrophobicity plant leaf blade being placed in non-oxidizing atmosphere and sintered, sintering temperature is more than 500 DEG C,
Heating rate is not more than 6 DEG C/min, and the carbon materials with plant leaf structure is made；
Step 2, using carbon materials as negative electrode, 3~9 min are electroplated in 0.2~0.6 mol/L solution of zinc sulfate, electric current is close
Spend for 0.01~0.20 A/cm2, untill one layer of zinc layers of carbon materials surface attachment；
Step 3, by the zinc-plated material in surface be immersed in silicon fluoride volume fraction be 10%~24% aqueous isopropanol in, leaching
Bubble is more than 6 days, and immersion takes out drying after terminating, and obtains petal-shaped zinc super hydrophobic surface.
Preferably, in step 1, described super-hydrophobicity plant leaf blade is rice-pudding leaf or lotus leaf, described non-oxidizing atmosphere
For argon gas or nitrogen, described sintering temperature is 600~800 DEG C, and heating rate is 2~5 DEG C/min.
Preferably, in step 2, described solution of zinc sulfate concentration is 0.3~0.5 mol/L, and electroplating time is 5~7
Min, current density are 0.05~0.11 A/cm2。
Preferably, in step 3, the volume fraction of described silicon fluoride is 14%~20%, and soak time is 6~11 days.
Compared with prior art, beneficial effect is the present invention：（1）Prepared zinc surface has blade surface classification knot
Structure, the reference of high level improve waterproof absorption and the anti-corrosion capability of zinc coating naturally, with excellent ultra-hydrophobicity.
（2）Methods described is simple, stably, it is practical, the zinc film of preparation is fine and close, is combined with matrix, good luster.
Brief description of the drawings
Fig. 1 is the super-hydrophobic phenomenon of rice-pudding leaf.
Fig. 2 is the low range stereoscan photograph of rice-pudding leaf surface microstructure.
Fig. 3 is the high magnification stereoscan photograph of rice-pudding leaf surface microstructure.
Fig. 4 is obtained zinc surface material object photo in the embodiment of the present invention 1.
Fig. 5 is the X diffracting spectrums of obtained zinc surface in the embodiment of the present invention 1.
Fig. 6 is the stereoscan photograph of obtained zinc surface microstructure in the embodiment of the present invention 1.
Fig. 7 is the contact angle photo of obtained zinc surface and water in the embodiment of the present invention 1.
Embodiment
The present invention is described in further detail with reference to embodiment and accompanying drawing.
The present invention using super-hydrophobicity plant leaf blade is template, and it is sintered in non-oxidizing atmosphere, blade during sintering
In organic matter decompose, oxygen, hydrogen, nitrogen and part carbon are changed into gaseous volatilization, and most carbons therein are then protected
Stay, so as to first obtain carbon materials.This carbon can retain the micron-sized mastoid process of blade surface, but can not retain nanoscale
Petal-shaped thin slice, thin slice sintering when disappear totally.Using carbon materials as cathode of electrolytic tank, carried out in solution of zinc sulfate
Plating, the zinc coating of layer can be obtained on its surface.The zinc coat can further retain mastoid process structure.Simultaneously because plating
The particularity of zinc, zinc can be grown in each mastoid process with petal-shaped, the petal-shaped thin slice of disappearance is recovered, so as to be had
There is the petal-shaped zinc of blade hierarchy.In the silicon fluoride solution of low-surface-energy in immersion process, silicon fluoride leads to the zinc surface
Cross hydrolysis and polycondensation forms very thin coating in Zinc Deposit.When water falls on zinc surface, in petal-shaped sheet gaps
Air can be locked, and one layer of very thin air layer is formed between water and zinc surface, and water only contacts with tab projection tip point, surface
Adhesion power is very weak, therefore water can congeal into the globule under surface tension effects, and can arbitrarily be rolled in zinc surface, so as to realize
Super-hydrophobicity.
The present invention uses electrogalvanizing, compared to the electro-coppering in plant leaf blade template（It is not limited to copper, including other metal materials
Material）There is very big advantage.All it is in fine particle shape, with leaf though copper can form trickleer structure in mastoid process during electro-coppering
The natural petal-shaped thin slice difference of piece is very big, and the degree that such copper plate retains blade hierarchy is relatively low.And electrogalvanizing can shape
Into the petal-shaped thin slice very much like with blade, it retains blade hierarchy degree and greatly improved.
The present invention compared in blade template by dipping solution, sintering prepare copper film method have it is bigger excellent
Gesture.The copper of preparation is only capable of the mastoid process structure for retaining blade, it is impossible to retains supramastoid fine structure, can not be formed new trickle
Structure.
Embodiment 1
Step 1, dry palm leaf is placed in argon gas atmosphere stove and is heated to 800 DEG C with 2 DEG C/min of heating rate, be made
Carbon materials with palm leaf microtexture；
Step 2, the cathode electrode using carbon materials as electrolytic cell, is electroplated, solution of zinc sulfate is dense in solution of zinc sulfate
Spend and use 0.09 A/cm for 0.3 mol/L, current density2, it is 5 min to control electroplating time, obtains petal-shaped zinc surface；
Step 3, by the zinc-plated material in surface be immersed in silicon fluoride volume fraction be 14% aqueous isopropanol in, soak 6 days
Take out and dry afterwards, petal-shaped zinc super hydrophobic surface is made；
Fig. 1 is the super-hydrophobic phenomenon of rice-pudding leaf, it is seen that water droplet forms spherical on rice-pudding leaf surface, illustrates that rice-pudding leaf has excellent hydrophobicity
Energy.
Fig. 2 is the low range stereoscan photograph of rice-pudding leaf surface microstructure, it is seen that rice-pudding leaf surface distributed has micron order newborn
It is prominent.
Fig. 3 is the high magnification stereoscan photograph of rice-pudding leaf surface microstructure, it is seen that nanometer is distributed with again in each mastoid process
A kind of hierarchy is presented in level petal-shaped thin slice, rice-pudding leaf surface.
Fig. 4 is zinc surface material object photo made from plating, it is seen that forms one layer of argenteous zinc coat in material surface.
Fig. 5 is the X diffracting spectrums of obtained zinc surface, it is known that the material is zinc.
Fig. 6 is the stereoscan photograph of obtained zinc surface microstructure, it is seen that mastoid process, and each breast is distributed with zinc surface
It is prominent that petal-shaped thin slice above is distributed with again, the hierarchy very much like with rice-pudding leaf is showed, the structure has for zinc surface material
There is ultra-hydrophobicity to play a key effect.
Fig. 7 is the contact angle photo of obtained zinc surface and water, θContact angle=167 °, reach super-hydrophobicity.
Embodiment 2
Step 1, dry palm leaf is placed in argon gas atmosphere stove and is heated to 600 DEG C with 5 DEG C/min of heating rate, be made
Carbon materials with palm leaf microtexture；
Step 2, the cathode electrode using carbon materials as electrolytic cell, is electroplated, solution of zinc sulfate is dense in solution of zinc sulfate
Spend and use 0.05 A/cm for 0.5 mol/L, current density2, it is 7 min to control electroplating time, obtains petal-shaped zinc surface；
Step 3, by the zinc-plated material in surface be immersed in silicon fluoride volume fraction be 20% aqueous isopropanol in, soak 11 days
Take out and dry afterwards, petal-shaped zinc super hydrophobic surface is made.
Embodiment 3
Step 1, dry lotus leaf is placed in argon gas atmosphere stove and is heated to 700 DEG C with 3 DEG C/min of heating rate, be made
Carbon materials with lotus leaf microtexture；
Step 2, the cathode electrode using carbon materials as electrolytic cell, is electroplated, solution of zinc sulfate is dense in solution of zinc sulfate
Spend and use 0.11 A/cm for 0.4 mol/L, current density2, it is 6 min to control electroplating time, obtains petal-shaped zinc surface；
Step 3, by the zinc-plated material in surface be immersed in silicon fluoride volume fraction be 17% aqueous isopropanol in, soak 8 days
Take out and dry afterwards, petal-shaped zinc super hydrophobic surface is made.
Claims (4)
1. the method for petal-shaped zinc super hydrophobic surface is prepared using plant leaf blade template, it is characterised in that comprise the following steps that：
Step 1, dry super-hydrophobicity plant leaf blade being placed in non-oxidizing atmosphere and sintered, sintering temperature is more than 500 DEG C,
Heating rate is not more than 6 DEG C/min, and the carbon materials with plant leaf structure is made；
Step 2, using carbon materials as negative electrode, 3~9 min are electroplated in 0.2~0.6 mol/L solution of zinc sulfate, electric current is close
Spend for 0.01~0.20 A/cm2, to carbon materials surface attachment zinc layers；
Step 3, the zinc-plated material in surface is immersed in the aqueous isopropanol that volume fraction is 10%~24% silicon fluoride, immersion
More than 6 days, immersion took out drying after terminating, and obtains petal-shaped zinc super hydrophobic surface.
2. according to the method for claim 1, it is characterised in that：In step 1, described super-hydrophobicity plant leaf blade is rice-pudding leaf
Or lotus leaf, described non-oxidizing atmosphere are argon gas or nitrogen, described sintering temperature is 600~800 DEG C, heating rate 2
~5 DEG C/min.
3. according to the method for claim 1, it is characterised in that：In step 2, described solution of zinc sulfate concentration be 0.3~
0.5 mol/L, electroplating time are 5~7 min, and current density is 0.05~0.11 A/cm2。
4. according to the method for claim 1, it is characterised in that：In step 3, the volume fraction of described silicon fluoride is 14%
~20%, soak time is 6~11 days.
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| CN201710847729.6A CN107675223B (en) | 2017-09-19 | 2017-09-19 | Method for preparing petaloid zinc super-hydrophobic surface by using plant leaf template |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109402570A (en) * | 2018-12-12 | 2019-03-01 | 深圳朗昇贸易有限公司 | Metal protection system based on nano-array |
| CN109680312A (en) * | 2019-01-24 | 2019-04-26 | 南京理工大学 | The method for plating the preparation super-hydrophobic Zinc material of sheet as template electric using natural timber |
| CN109680308A (en) * | 2019-01-24 | 2019-04-26 | 南京理工大学 | The method for plating the preparation hydrophobic nickel material of graininess as template electric using natural timber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911644A (en) * | 2015-04-15 | 2015-09-16 | 中国石油大学(华东) | Preparation method of superhydrophobic galvanizing coating on steel surface |
| CN105256342A (en) * | 2015-10-19 | 2016-01-20 | 华南理工大学 | Copper-based super-hydrophobic surface and preparation method thereof |
| CN106591896A (en) * | 2016-12-06 | 2017-04-26 | 南京理工大学 | Method for preparing super-hydrophobic copper surface of plant leaf structure |
| CN106757224A (en) * | 2016-12-01 | 2017-05-31 | 吉林大学 | A kind of preparation method with the anisotropic fine copper super hydrophobic surface of wetting |
-
2017
- 2017-09-19 CN CN201710847729.6A patent/CN107675223B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911644A (en) * | 2015-04-15 | 2015-09-16 | 中国石油大学(华东) | Preparation method of superhydrophobic galvanizing coating on steel surface |
| CN105256342A (en) * | 2015-10-19 | 2016-01-20 | 华南理工大学 | Copper-based super-hydrophobic surface and preparation method thereof |
| CN106757224A (en) * | 2016-12-01 | 2017-05-31 | 吉林大学 | A kind of preparation method with the anisotropic fine copper super hydrophobic surface of wetting |
| CN106591896A (en) * | 2016-12-06 | 2017-04-26 | 南京理工大学 | Method for preparing super-hydrophobic copper surface of plant leaf structure |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109402570A (en) * | 2018-12-12 | 2019-03-01 | 深圳朗昇贸易有限公司 | Metal protection system based on nano-array |
| CN109680312A (en) * | 2019-01-24 | 2019-04-26 | 南京理工大学 | The method for plating the preparation super-hydrophobic Zinc material of sheet as template electric using natural timber |
| CN109680308A (en) * | 2019-01-24 | 2019-04-26 | 南京理工大学 | The method for plating the preparation hydrophobic nickel material of graininess as template electric using natural timber |
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