CN105063572B - A kind of preparation method of the bionical hydrophobic graphene film of aluminum alloy surface - Google Patents
A kind of preparation method of the bionical hydrophobic graphene film of aluminum alloy surface Download PDFInfo
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- CN105063572B CN105063572B CN201510590022.2A CN201510590022A CN105063572B CN 105063572 B CN105063572 B CN 105063572B CN 201510590022 A CN201510590022 A CN 201510590022A CN 105063572 B CN105063572 B CN 105063572B
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Abstract
The invention belongs to metal material surface to modify field, it is related to a kind of method that bionical hydrophobic graphene is constructed on alloy matrix aluminum, micro-structural processing is first carried out to aluminum alloy surface using surface mechanical manufacturing technology, is prepared for the array surface texture with bionical convex-concave structure；The oxide-film for removing surface is cleaned to copper foil substrate again；Then, using chemical vapour deposition technique on copper foil substrate growth in situ graphene, copper foil substrate is finally removed using the method for chemical etching, and transfers graphene to aluminum alloy surface.The inventive method is simple and easy, reappearance is high and durability, prepared product shows higher stability and durability at ambient temperature, the present invention to later aluminium alloy use and development has great importance, also provide reference to prepare hydrophobic self-cleaning surface on other metallic matrixes.Meanwhile it can also promote the extensive use of graphene itself.
Description
Technical field
The invention belongs to metal material surface to modify field, and in particular to one kind is constructed bionical hydrophobic on alloy matrix aluminum
The method of graphene film.
Background technology
Aluminium alloy due to density it is small, be easy to processing, antiseptic property is good and the distinguishing feature such as mechanical strength height, answer extensively
For in modern industry.However, aluminum alloy surface is but highly susceptible to the corrosion of chlorion in neutral solution, aluminium alloy is limited
Application.Therefore, it is necessary to prepare the aluminum alloy materials with surface super hydrophobic property.On the one hand, super-hydrophobic surface structure
The Anticorrosive Character of aluminium alloy can be improved by being formed, and extend the service life of aluminium alloy；On the other hand, answering for aluminium alloy can be extended
With scope, aluminium alloy is assigned with characteristics such as not viscous, automatically cleaning and drag reductions, extends aluminium alloy in navigation and aircraft application material
Application.
In nature, the surface of many animals and plants all has super-hydrophobic property, and the automatically cleaning property of leaf surface of plant is most
Representative is lotus leaf.The micron and nanoscale structures that lotus leaf surface is distributed by stratified random form, and water is this hydrophobic
Surface has larger contact angle and less roll angle, and the unique texture imparts the excellent ultra-hydrophobicity of lotus leaf surface.
Because aluminum alloy surface is high energy surface, its surface can pass through following two modes by hydrophilic steering is hydrophobic：It is a kind of
It is that the special appearance that array coarse structure is carried out to its surface is built, realizes hydrophobicity；Another kind is to use low-surface-energy material
Modified, form the diaphragm with hydrophobic performance.
Graphene is a kind of New Two Dimensional carbon atom material, due to its high conductivity, the high optical lens in visible-range
Lightness, excellent carrier mobility, chemical inertness, heat endurance and high machinery are slight etc., cause the extensive of Chinese and overseas scholars
Concern.Because graphene can have an impact to the wetability of material surface, the flexibility that many scholars attempt to graphene is constructed
The bionic surface of similar lotus leaf surface, while surface super hydrophobic is realized, assign the other properties of material surface, such as Anticorrosive Character
With wearability etc..
The preparation method of bionic super-hydrophobic surface is a lot, generally there is chemical etching method, chemical vapour deposition technique both at home and abroad
(CVD), micro-arc oxidation, laser ablation method, sol-gel process, template and anodizing etc., wherein, CVD is one
The method that kind prepares high-quality graphene, concrete technology is the metal that the mixed gas of methane and hydrogen is passed into high-temperature heating
Substrate surface, cooled down after reacting certain time under the high temperature conditions, will be formed in substrate surface in cooling procedure
Several layers or single-layer graphene, growth two parts are dissolved and spread in substrate comprising carbon atom during this.The advantages of this method
It is to carry out at a lower temperature, so as to reduce the consumption of energy in preparation process.Also, graphene can lead to substrate
The method for crossing chemical attack is easily separated, and is advantageous to subsequently be processed graphene.
CVD is prepared into the graphene film with low-surface-energy with building array coarse structure in aluminum alloy surface
Technology organically combines, and constructs out the bionical hydrophobic surface of similar lotus leaf structure in aluminum alloy surface, realizes that aluminum alloy surface is hydrophobic
Self-cleaning characteristic, to later aluminium alloy use and development has great importance, also to be prepared on other metallic matrixes
Hydrophobic self-cleaning surface provides reference.Meanwhile it can also promote the extensive use of graphene itself.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of the bionical hydrophobic graphene film of aluminum alloy surface, improves
The hydrophobicity of aluminum alloy surface.
The purpose of the present invention is achieved through the following technical solutions：
A, the processing of aluminum alloy substrate：The oxide layer of aluminum alloy surface is removed, and is array cylinder by its Surface Machining
Shape convex closure structure, a diameter of 100 μm or 250 μm of its convex closure, a height of 10 μm of convex closure, corresponding adjacent convex closure spacing is respectively 200 μ
M and 350 μm；
B, the preparation of graphene film：
B1, copper foil substrate processing：
The surface clean of copper foil substrate：At room temperature, cleaned, placed into absolute ethyl alcohol, acetone and distilled water decontamination successively
Concentration is to soak 5min in 10%~20% hydrochloric acid solution, washes and dries after removing its surface oxide layer；
Annealing：Made annealing treatment in anti-oxidation atmosphere, annealing time 0.5h, temperature is 1000 DEG C；
B2, process for preparing graphenes by chemical vapour deposition film：Volume ratio is passed through into pipe reaction stove as 1：1 methane,
Hydrogen gas mixture, graphene film is grown on copper foil substrate surface, the flow rate for being passed through mixed gas is 10mm/s, reaction temperature
Spend for 1030 DEG C, room temperature is cooled to after the completion of reaction；
C, the wet method transfer of graphene film：
C1, surface made from taking-up step B2 has the copper foil of graphene film from reacting furnace, in graphene film table
The strata methyl methacrylate of face spin coating one, and solidify in 100 DEG C, the concentration of the polymethyl methacrylate is 50mg/mL,
Solvent is chlorobenzene or methyl phenyl ethers anisole；
C2, the etching agent using concentration as 200mg/mL etch copper foil substrate completely, then, with distilled water by after etching
The graphene film of compound polymethyl methacrylate soaking and washing repeatedly, removes remaining etching agent；
C3, by the graphene film of compound polymethyl methacrylate covering obtained aluminum alloy substrate table in step
Face, and 100 DEG C of solidifications make graphene film and aluminium alloy compound one；
D, the removal of polymethyl methacrylate layers：Compound polymethyl methacrylate, the graphene that step C3 is obtained
The aluminium alloy of film is inserted in acetone soln, removes polymethyl methacrylate layers.
Anti-oxidation atmosphere described in step B1 is that volume ratio is 1:1 hydrogen, argon gas mixed gas.
The growth time of the growth graphene film of copper foil substrate surface described in step B2 is 40min.
Etching agent described in step C2 is ferric chloride aqueous solutionses.
Compared with prior art, beneficial effects of the present invention are：
(1) the hydrophobicity graphene film with micro-meter scale bilayer hierarchy has been constructed in aluminum alloy substrate, its
Uniformly, closely, the made bionical hydrophobic graphene film of aluminum alloy surface shows higher stability to hydrophobic structure at room temperature
And durability.
(2) it is 88 ± 2 ° without the al alloy specimens contact angle of any Laser Processing processing；When processing convex closure a diameter of 250
μm when, contact angle be 118 ± 2 °, after graphene modified, the contact angle of aluminum alloy material surface further improves, and increases to
130 ± 2 °；When processing convex closure is a diameter of 100 μm, contact angle has reached 115 ± 2 °, after graphene modified, aluminium alloy
The contact angle of material surface increases 128 ° ± 2 °.
(3) with common graphene prepare and hydrophobic structure construction method compared with, the method is simple and easy, reappearance is high and
With durability, the transfer of graphene is prepared by the Surface Machining to metal base and CVD, is constructed out with specific structure
Bionic super-hydrophobic surface, realize the structure-controllable of bionical hydrophobic graphene film.
Brief description of the drawings
Fig. 1 a scheme for copper foil substrate surface SEM of the present invention.
Fig. 1 b are the graphene of copper foil substrate surface growth of the present invention without salt low-kappa number in 3000 times of enlargement ratios
Under SEM figure.
Fig. 1 c are the graphene of copper foil substrate surface growth of the present invention without salt low-kappa number in 6000 times of enlargement ratios
Under SEM figure.
Fig. 1 d are the graphene of copper foil substrate surface growth of the present invention without salt low-kappa number in 10000 times of enlargement ratios
Under SEM figure.
Fig. 2 a are the graphene of copper foil substrate surface growth of the present invention through salt low-kappa number under 500 times of enlargement ratios
SEM schemes.
Fig. 2 b are the graphene of copper foil substrate surface growth of the present invention through salt low-kappa number under 3000 times big multiplying power
SEM schemes.
Fig. 2 c are the graphene of copper foil substrate surface growth of the present invention through salt low-kappa number under 6000 times of enlargement ratios
SEM figure.
Fig. 2 d are under 10000 times of enlargement ratios of graphene of copper foil substrate surface growth of the present invention through salt low-kappa number
SEM schemes.
Fig. 3 a are that the present invention constructs SEM figure of the aluminum alloy surface under 50 times of enlargement ratios after bionical hydrophobic graphene, its
In, a diameter of 250 μm of convex closure.
Fig. 3 b are that the present invention constructs SEM figure of the aluminum alloy surface under 100 times of enlargement ratios after bionical hydrophobic graphene, its
In, a diameter of 250 μm of convex closure.
Fig. 3 c are that the present invention constructs SEM figure of the aluminum alloy surface under 50 times of enlargement ratios after bionical hydrophobic graphene, its
In, a diameter of 100 μm of convex closure.
Fig. 3 d are that the present invention constructs SEM figure of the aluminum alloy surface under 100 times of enlargement ratios after bionical hydrophobic graphene, its
In, a diameter of 100 μm of convex closure.
Fig. 4 is the static contact angle that the present invention constructs aluminum alloy surface after bionical hydrophobic graphene.
Embodiment
The present invention copies double-deck hierarchy possessed by the animals and plants such as lotus leaf, rose, beetle surface, first using table
Face mechanical manufacturing technology carries out micro-structural processing to aluminum alloy surface, is prepared for having the array surface of bionical convex-concave structure to tie
Structure；The oxide-film for removing surface is cleaned to copper foil substrate again；Then, using CVD on copper foil substrate growth in situ graphene,
Copper foil substrate is finally removed using the method for chemical etching, and transfers graphene to aluminum alloy surface.The present invention adds machinery
Work builds array coarse structure surface and the dual mode of superficial growth low-surface-energy graphene is combined, the structure on aluminium alloy
Build hydrophobic surface.
Embodiments of the invention are described below in conjunction with the accompanying drawings, but the invention is not limited in this：
Embodiment 1
A kind of preparation method of the bionical hydrophobic graphene film of aluminum alloy surface, specifically includes following steps：
Aluminum alloy machinery is processed：The aluminium alloy for being 2024 from the trade mark is substrate, and bionical micro- knot is carried out in aluminum alloy surface
Structure is processed.First, aluminum alloy substrate is cut into the batten that size is 15 × 15 × 1mm.Then, the aluminium after cutting is closed
Gold surface is polished with the sand paper of 400-2000 mesh, it is therefore an objective to removes the oxide layer on surface.Then, it is processed by shot blasting, and
It is cleaned by ultrasonic 10min in absolute ethyl alcohol, 2h is finally dried in 80 DEG C of vacuum tank.Finally, using mechanical manufacturing technology,
Aluminum alloy surface processes the cylindric convex closure structure of array, and a diameter of 100 μm of columned convex closure or 250 μm, convex closure is high
For 10 μm, corresponding adjacent convex closure spacing is respectively 200 μm and 350 μm.
Copper foil substrate processing：In order to obtain the single-layer graphene of high quality in copper foil substrate deposition, it is necessary to which copper foil is carried out
Pretreatment.First, copper foil substrate is sequentially placed into absolute ethyl alcohol, acetone and deionized water and cleaned, it is therefore an objective to remove copper
Paper tinsel impurity on substrate surface and pollutant.Then, copper foil substrate is placed in the hydrochloric acid solution that concentration is 10% and soaked, processing time
For 5min, it is therefore an objective to remove the oxide and impurity of copper foil substrate surface.Then, the copper foil after surface treatment is washed,
And 2h is dried in 80 DEG C of exsiccators.Finally, copper foil is made annealing treatment at 1000 DEG C, while is passed through volume ratio as 1：1
Hydrogen, argon gas mixed airflow, annealing time 0.5h.
CVD prepares graphene：The CVD that the preparation of graphene is mainly carried out using G-CVD growth apparatus.First,
Copper foil substrate is handled.Copper foil is folded with tweezers, makes copper foil that the shape of a box be presented.When substrate processing completes it
Afterwards, the constant temperature zone position it being put into from sample introduction end in high-temperature tubular reacting furnace, sample tighten sample introduction baffle plate after putting well, and
Shift whole body of heater onto inlet end 10cm or so place, turn on the power air switch.Then, start vavuum pump, carry out vacuumizing place
Reason.After vacuum values are reduced to below 1Pa, computer graphene growth automatic control system is opened, growth time parameter is set
It is 1030 DEG C and CH for 30min, growth temperature parameter4/H2(purity 99.999%, volume ratio 1：1) stream of mixed airflow
Rate parameter is 10mm/s.Then, system is started to warm up, and heating rate is controlled within 15 DEG C/min, H in temperature-rise period2With
10mm/s flow rate is passed through, and temperature keeps 10min after being raised to 1030 DEG C of setting value；CH is passed through with 10mm/s flow rate4After air-flow,
Start to grow graphene, growth time 40min.At the end of this process, growth system is cooled.In order to realize stone
Reaction equation cools rapidly after black alkene deposition, and the system mainly takes plug-type input mode, can be used cooperatively fan and dry
Accelerate cooling, it is this to be designed to improve graphene deposition efficiency.So, push body of heater open heating zone, be then shut off heating and open
Close.Continue to be passed through the hydrogen and methane of same flow, it is noted that bell can not be opened in temperature-fall period.When temperature drops to room temperature
Afterwards, the stop button on software is clicked on, stopping is passed through methane and hydrogen, while presses pump stop button, samples, bolt down procedure.
After sample successfully takes out, injection port valve is tightened, vavuum pump is opened and vacuumizes again, to be reduced to background once again true when vacuum values
After sky, vacuum pump switch is closed.Then to parameter and data are preserved.Finally close software, computer and all power supplys.
The transfer of graphene film：Graphene transfer mainly takes PMMA wet method to shift.First, graphene will be grown
Copper foil takes out from reacting furnace, then one layer of PMMA of spin coating on surface (solvent be chlorobenzene, concentration 50mg/mL) again.Spin coating
Machine spin speed is 3000 turns/min, and the time is set as 60s.Then in solidifying on hot plate, 100 DEG C of temperature, time 5min.Connect
, mixed film is performed etching to (solvent be water, concentration 200mg/mL) in ammonium persulfate solution, etched at room temperature
12h, it is therefore an objective to be etched completely away copper substrate；PMMA/ graphenes are pulled out from etching agent, be placed in deionization rinse it is several
All over the unnecessary etching agent of removing.PMMA/ graphenes are picked up with aluminum alloy substrate, after room temperature is dried, is placed on 100 DEG C of hot plates and handles
10min, graphene and substrate is set fully to contact and bond.Obtained PMMA/ graphene/aluminum alloys are inserted in acetone soln,
12h is placed at room temperature, in order to removes PMMA.Finally, graphene is transferred to target aluminum alloy substrate surface, is closed with reference to aluminium
The array convex-concave structure that gold surface itself has, and then it is prepared for hydrophobic self-cleaning graphenic surface in aluminium alloy.
Embodiment 2
A kind of preparation method of the bionical hydrophobic graphene film of aluminum alloy surface, specifically includes following steps：
Aluminum alloy machinery is processed：The aluminium alloy for being 2024 from the trade mark is substrate, and bionical micro- knot is carried out in aluminum alloy surface
Structure is processed.First, aluminum alloy substrate is cut into the batten that size is 15 × 15 × 1mm.Then, the aluminium after cutting is closed
Gold surface is polished with the sand paper of 400-2000 mesh, it is therefore an objective to removes the oxide layer on surface.Then, it is processed by shot blasting, and
It is cleaned by ultrasonic 10min in absolute ethyl alcohol, 2h is finally dried in 80 DEG C of vacuum tank.Finally, using mechanical manufacturing technology,
Aluminum alloy surface processes the cylindric convex closure structure of array, and a diameter of 100 μm of columned convex closure or 250 μm, convex closure is high
For 10 μm, corresponding adjacent convex closure spacing is respectively 200 μm and 350 μm.
Copper foil substrate processing：In order to obtain the single-layer graphene of high quality in copper foil substrate deposition, it is necessary to which copper foil is carried out
Pretreatment.First, copper foil substrate is sequentially placed into absolute ethyl alcohol, acetone and deionized water and cleaned, it is therefore an objective to remove copper
Paper tinsel impurity on substrate surface and pollutant.Then, copper foil substrate is placed in the hydrochloric acid solution that concentration is 20% and soaked, processing time
For 5min, it is therefore an objective to remove the oxide and impurity of copper foil substrate surface.Then, the copper foil after surface treatment is washed,
And 2h is dried in 80 DEG C of exsiccators.Finally, copper foil is made annealing treatment at 1000 DEG C, while is passed through volume ratio as 1：1
Hydrogen, argon gas mixed airflow, annealing time 0.5h.
CVD prepares graphene：The CVD that the preparation of graphene is mainly carried out using G-CVD growth apparatus.First,
Copper foil substrate is handled.Copper foil is folded with tweezers, makes copper foil that the shape of a box be presented.When substrate processing completes it
Afterwards, the constant temperature zone position it being put into from sample introduction end in high-temperature tubular reacting furnace, sample tighten sample introduction baffle plate after putting well, and
Shift whole body of heater onto inlet end 10cm or so place, turn on the power air switch.Then, start vavuum pump, carry out vacuumizing place
Reason.After vacuum values are reduced to below 1Pa, computer graphene growth automatic control system is opened, growth time parameter is set
It is 1030 DEG C and CH for 30min, growth temperature parameter4/H2(purity 99.999%, volume ratio 1：1) stream of mixed airflow
Rate parameter is 10mm/s.Then, system is started to warm up, and heating rate is controlled within 15 DEG C/min, H in temperature-rise period2With
10mm/s flow rate is passed through, and temperature keeps 10min after being raised to 1030 DEG C of setting value；CH is passed through with 10mm/s flow rate4After air-flow,
Start to grow graphene, growth time 40min.At the end of this process, growth system is cooled.In order to realize stone
Reaction equation cools rapidly after black alkene deposition, and the system mainly takes plug-type input mode, can be used cooperatively fan and dry
Accelerate cooling, it is this to be designed to improve graphene deposition efficiency.So, push body of heater open heating zone, be then shut off heating and open
Close.Continue to be passed through the hydrogen and methane of same flow, it is noted that bell can not be opened in temperature-fall period.When temperature drops to room temperature
Afterwards, the stop button on software is clicked on, stopping is passed through methane and hydrogen, while presses pump stop button, samples, bolt down procedure.
After sample successfully takes out, injection port valve is tightened, vavuum pump is opened and vacuumizes again, to be reduced to background once again true when vacuum values
After sky, vacuum pump switch is closed.Then to parameter and data are preserved.Finally close software, computer and all power supplys.
The transfer of graphene film：Graphene transfer mainly takes PMMA wet method to shift.First, graphene will be grown
Copper foil takes out from reacting furnace, then one layer of PMMA of spin coating on surface (solvent be chlorobenzene, concentration 50mg/mL) again.Spin coating
Machine spin speed is 3000 turns/min, and the time is set as 60s.Then in solidifying on hot plate, 100 DEG C of temperature, time 5min.Connect
, mixed film is performed etching to (solvent be water, concentration 200mg/mL) in ammonium persulfate solution, etched at room temperature
12h, it is therefore an objective to be etched completely away copper substrate；PMMA/ graphenes are pulled out from etching agent, be placed in deionization rinse it is several
All over the unnecessary etching agent of removing.PMMA/ graphenes are picked up with aluminum alloy substrate, after room temperature is dried, is placed on 100 DEG C of hot plates and handles
10min, graphene and substrate is set fully to contact and bond.Obtained PMMA/ graphene/aluminum alloys are inserted in acetone soln,
12h is placed at room temperature, in order to removes PMMA.Finally, graphene is transferred to target aluminum alloy substrate surface, is closed with reference to aluminium
The array convex-concave structure that gold surface itself has, and then it is prepared for hydrophobic self-cleaning graphenic surface in aluminium alloy.
Embodiment 3
A kind of preparation method of the bionical hydrophobic graphene film of aluminum alloy surface, specifically includes following steps：
Aluminum alloy machinery is processed：The aluminium alloy that this patent is 2024 from the trade mark is substrate, is imitated in aluminum alloy surface
Raw micro-structural processing.First, aluminum alloy substrate is cut into the batten that size is 15 × 15 × 1mm.Then, after to cutting
Aluminum alloy surface polished with the sand paper of 400-2000 mesh, it is therefore an objective to remove the oxide layer on surface.Then, it is polished place
Reason, and it is cleaned by ultrasonic 10min in absolute ethyl alcohol, 2h is finally dried in 80 DEG C of vacuum tank.Finally, using machining skill
Art, the cylindric convex closure structure of array is processed in aluminum alloy surface, it is a diameter of 100 μm of columned convex closure or 250 μm, convex
A height of 10 μm are wrapped, corresponding adjacent convex closure spacing is respectively 200 μm and 350 μm.
Copper foil substrate processing：In order to obtain the single-layer graphene of high quality in copper foil substrate deposition, it is necessary to which copper foil is carried out
Pretreatment.First, copper foil substrate is sequentially placed into absolute ethyl alcohol, acetone and deionized water in order and cleaned, it is therefore an objective to
Remove copper foil impurity on substrate surface and pollutant.Then, copper foil substrate is placed in the hydrochloric acid solution that concentration is 10% and soaked, located
The reason time is 5min, it is therefore an objective to removes the oxide and impurity of copper foil substrate surface.Then, the copper foil after surface treatment is carried out
Washing, and 2h is dried in 80 DEG C of exsiccators.Finally, copper foil is made annealing treatment at 1000 DEG C, while is passed through volume ratio
For 1：1 hydrogen, argon gas mixed airflow, annealing time 0.5h.
CVD prepares graphene：In this patent, the preparation of graphene is mainly carried out using G-CVD growth apparatus
CVD.First, copper foil substrate is handled.Copper foil is folded with tweezers, makes copper foil that the shape of a box be presented.Work as lining
After bottom reason is completed, the constant temperature zone position that it is put into from sample introduction end in high-temperature tubular reacting furnace, sample will enter after putting well
Sample baffle plate is tightened, and shifts whole body of heater onto inlet end 10cm or so place, turns on the power air switch.Then, vavuum pump is started,
Carry out vacuumize process.After vacuum values are reduced to below 1Pa, computer graphene growth automatic control system is opened, is set
Growth time parameter is 30min, growth temperature parameter is 1030 DEG C and CH4/H2(purity 99.999%, volume ratio 1：1)
The flow rate parameters of mixed airflow are 10mm/s.Then, system is started to warm up, and heating rate is controlled within 15 DEG C/min, heating
During H2It is passed through with 10mm/s flow rate, temperature keeps 10min after being raised to 1030 DEG C of setting value；It is passed through with 10mm/s flow rate
CH4After air-flow, start to grow graphene, growth time 40min.At the end of this process, growth system is cooled.
In order to realize, reaction equation cools rapidly after graphene deposition, and the system mainly takes plug-type input mode, and can coordinate makes
Dried with fan and accelerate cooling, it is this to be designed to improve graphene deposition efficiency.So, body of heater is pushed open heating zone, then
Close heater switch.Continue to be passed through the hydrogen and methane of same flow, it is noted that bell can not be opened in temperature-fall period.Work as temperature
After dropping to room temperature, the stop button on software is clicked on, stopping is passed through methane and hydrogen, while presses pump stop button, samples,
Bolt down procedure.After sample successfully takes out, injection port valve is tightened, vavuum pump is opened and vacuumizes again, when vacuum values drop once again
It is low to after base vacuum, vacuum pump switch is closed.Then to parameter and data are preserved.Finally close software, computer and
All power supplys.
The transfer of graphene film：Graphene transfer mainly takes PMMA wet method to shift.First, graphene will be grown
Copper foil takes out from reacting furnace, then one layer of PMMA of spin coating on surface (solvent be chlorobenzene, concentration 50mg/mL) again.Spin coating
Machine spin speed is 3000 turns/min, and the time is set as 60s.Then in solidifying on hot plate, 100 DEG C of temperature, time 5min.Connect
, mixed film is performed etching to (solvent be water, concentration 200mg/mL) in liquor ferri trichloridi, etched at room temperature
12h, it is therefore an objective to be etched completely away copper substrate；PMMA/ graphenes are pulled out from etching agent, be placed in deionization rinse it is several
All over the unnecessary etching agent of removing.PMMA/ graphenes are picked up with aluminum alloy substrate, after room temperature is dried, is placed on 100 DEG C of hot plates and handles
10min, graphene and substrate is set fully to contact and bond.Obtained PMMA/ graphene/aluminum alloys are inserted in acetone soln,
12h is placed at room temperature, in order to removes PMMA.Finally, graphene is transferred to target aluminum alloy substrate surface, is closed with reference to aluminium
The array convex-concave structure that gold surface itself has, and then it is prepared for hydrophobic self-cleaning graphenic surface in aluminium alloy.
Embodiment 4
A kind of preparation method of the bionical hydrophobic graphene film of aluminum alloy surface, specifically includes following steps：
Aluminum alloy machinery is processed：The aluminium alloy that this patent is 2024 from the trade mark is substrate, is imitated in aluminum alloy surface
Raw micro-structural processing.First, aluminum alloy substrate is cut into the batten that size is 15 × 15 × 1mm.Then, after to cutting
Aluminum alloy surface polished with the sand paper of 400-2000 mesh, it is therefore an objective to remove the oxide layer on surface.Then, it is polished place
Reason, and it is cleaned by ultrasonic 10min in absolute ethyl alcohol, 2h is finally dried in 80 DEG C of vacuum tank.Finally, using machining skill
Art, the cylindric convex closure structure of array is processed in aluminum alloy surface, it is a diameter of 100 μm of columned convex closure or 250 μm, convex
A height of 10 μm are wrapped, corresponding adjacent convex closure spacing is respectively 200 μm and 350 μm.
Copper foil substrate processing：In order to obtain the single-layer graphene of high quality in copper foil substrate deposition, it is necessary to which copper foil is carried out
Pretreatment.First, copper foil substrate is sequentially placed into absolute ethyl alcohol, acetone and deionized water and cleaned, it is therefore an objective to remove copper
Paper tinsel impurity on substrate surface and pollutant.Then, copper foil substrate is placed in the hydrochloric acid solution that concentration is 10% and soaked, processing time
For 5min, it is therefore an objective to remove the oxide and impurity of copper foil substrate surface.Then, the copper foil after surface treatment is washed,
And 2h is dried in 80 DEG C of exsiccators.Finally, copper foil is made annealing treatment at 1000 DEG C, while is passed through volume ratio as 1：1
Hydrogen, argon gas mixed airflow, annealing time 0.5h.
CVD prepares graphene：In this patent, the preparation of graphene is mainly carried out using G-CVD growth apparatus
CVD.First, copper foil substrate is handled.Copper foil is folded with tweezers, makes copper foil that the shape of a box be presented.Work as lining
After bottom reason is completed, the constant temperature zone position that it is put into from sample introduction end in high-temperature tubular reacting furnace, sample will enter after putting well
Sample baffle plate is tightened, and shifts whole body of heater onto inlet end 10cm or so place, turns on the power air switch.Then, vavuum pump is started,
Carry out vacuumize process.After vacuum values are reduced to below 1Pa, computer graphene growth automatic control system is opened, is set
Growth time parameter is 30min, growth temperature parameter is 1030 DEG C and CH4/H2(purity 99.999%, volume ratio 1：1)
The flow rate parameters of mixed airflow are 10mm/s.Then, system is started to warm up, and heating rate is controlled within 15 DEG C/min, heating
During H2It is passed through with 10mm/s flow rate, temperature keeps 10min after being raised to 1030 DEG C of setting value；It is passed through with 10mm/s flow rate
CH4After air-flow, start to grow graphene, growth time 40min.At the end of this process, growth system is cooled.
In order to realize, reaction equation cools rapidly after graphene deposition, and the system mainly takes plug-type input mode, and can coordinate makes
Dried with fan and accelerate cooling, it is this to be designed to improve graphene deposition efficiency.So, body of heater is pushed open heating zone, then
Close heater switch.Continue to be passed through the hydrogen and methane of same flow, it is noted that bell can not be opened in temperature-fall period.Work as temperature
After dropping to room temperature, the stop button on software is clicked on, stopping is passed through methane and hydrogen, while presses pump stop button, samples,
Bolt down procedure.After sample successfully takes out, injection port valve is tightened, vavuum pump is opened and vacuumizes again, when vacuum values drop once again
It is low to after base vacuum, vacuum pump switch is closed.Then to parameter and data are preserved.Finally close software, computer and
All power supplys.
The transfer of graphene film：Graphene transfer mainly takes PMMA wet method to shift.First, graphene will be grown
Copper foil takes out from reacting furnace, then one layer of PMMA of spin coating on surface (solvent be methyl phenyl ethers anisole, concentration 50mg/mL) again.Spin coating
Machine spin speed is 3000 turns/min, and the time is set as 60s.Then in solidifying on hot plate, 100 DEG C of temperature, time 5min.Connect
, mixed film is performed etching to (solvent be water, concentration 200mg/mL) in ammonium persulfate solution, etched at room temperature
12h, it is therefore an objective to be etched completely away copper substrate；PMMA/ graphenes are pulled out from etching agent, be placed in deionization rinse it is several
All over the unnecessary etching agent of removing.PMMA/ graphenes are picked up with aluminum alloy substrate, after room temperature is dried, is placed on 100 DEG C of hot plates and handles
10min, graphene and substrate is set fully to contact and bond.Obtained PMMA/ graphene/aluminum alloys are inserted in acetone soln,
12h is placed at room temperature, in order to removes PMMA.Finally, graphene is transferred to target aluminum alloy substrate surface, is closed with reference to aluminium
The array convex-concave structure that gold surface itself has, and then it is prepared for hydrophobic self-cleaning graphenic surface in aluminium alloy.
Claims (4)
1. a kind of preparation method of the bionical hydrophobic graphene film of aluminum alloy surface, it is characterised in that comprise the following steps：
A, the processing of aluminum alloy substrate：The oxide layer of aluminum alloy surface is removed, and is that array is cylindric convex by its Surface Machining
Pack arrangement, a diameter of 100 μm or 250 μm of its convex closure, a height of 10 μm of convex closure, corresponding adjacent convex closure spacing be respectively 200 μm and
350μm；
B, the preparation of graphene film：
B1, copper foil substrate processing：
The surface clean of copper foil substrate：At room temperature, cleaned successively with absolute ethyl alcohol, acetone and distilled water decontamination, place into concentration
To soak 5min in 10%~20% hydrochloric acid solution, wash and dry after removing its surface oxide layer；
Annealing：Made annealing treatment in anti-oxidation atmosphere, annealing time 0.5h, temperature is 1000 DEG C；
B2, process for preparing graphenes by chemical vapour deposition film：Volume ratio is passed through into pipe reaction stove as 1：1 methane, hydrogen
Mixed gas, graphene film is grown on copper foil substrate surface, the flow rate for being passed through mixed gas is 10mm/s, and reaction temperature is
1030 DEG C, room temperature is cooled to after the completion of reaction；
C, the wet method transfer of graphene film：
C1, surface made from taking-up step B2 has the copper foil of graphene film from reacting furnace, is revolved on graphene film surface
Apply a strata methyl methacrylate, and in 100 DEG C of solidifications, the concentration of the polymethyl methacrylate is 50mg/mL, solvent
For chlorobenzene or methyl phenyl ethers anisole；
C2, the etching agent using concentration as 200mg/mL etch copper foil substrate completely, then, will be compound after etching with distilled water
The graphene film of polymethyl methacrylate soaking and washing repeatedly, removes remaining etching agent；
C3, by the graphene film of compound polymethyl methacrylate covering obtained aluminum alloy substrate surface in step, and
100 DEG C of solidifications make graphene film and aluminium alloy compound one；
D, the removal of polymethyl methacrylate layers：Compound polymethyl methacrylate, the graphene film that step C3 is obtained
Aluminium alloy insert in acetone soln, remove polymethyl methacrylate layers.
2. a kind of preparation method of the bionical hydrophobic graphene film of aluminum alloy surface according to claim 1, its feature exist
In the anti-oxidation atmosphere is that volume ratio is 1：1 hydrogen, argon gas mixed gas.
3. a kind of preparation method of the bionical hydrophobic graphene film of aluminum alloy surface according to claim 1, its feature exist
In the growth time of the growth graphene film of copper foil substrate surface described in step B2 is 40min.
4. a kind of preparation method of the bionical hydrophobic graphene film of aluminum alloy surface according to claim 1, its feature exist
In etching agent described in step C2 is ferric chloride aqueous solutionses.
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