A kind of high dispersive, the graphene coating of high corrosion resistant and preparation method
Technical field
The invention belongs to the technical field of coating preparation, there is provided a kind of high dispersive, the graphene coating of high corrosion resistant and system
Preparation Method.
Background technology
Graphene (Graphene) is a kind of two dimension (2D) material of novel single-layer laminated structure being made up of carbon atom, is
The hexangle type being made up of carbon atom with sp2 hybridized orbits is in the flat film of honeycomb lattice.Most attracted attention as 21 century by people
One of new material, graphene crystalline material have " to it is thin, to hard ", the characteristic such as excellent heat conductor and electron mobility.
Unique design feature makes its purposes cause the high expectation of people plus " extreme prominent " performance, and graphene is or will
Revolutionary great change is brought to society, research temperature is persistently overheating in the whole world!To graphene conduction, anti-corrosion, fire-retardant, heat conduction and
Colorful prospect has also been delineated in application in the functional paints such as high intensity.
Graphene coating is to utilize graphene high-specific surface area, Quick conductive, excellent chemical stability, the power of protrusion
Learn one of important uses of performance such as performance, high-termal conductivity.Graphene is used to that in coating pure graphene coating and graphite can be prepared
Alkene composite coating, the former is primarily referred to as pure graphene and plays the functional paint of the effects such as anticorrosion, conduction in metal surface;The latter
It is compound with fluoropolymer resin first to be primarily referred to as graphene, functional paint is then prepared with composite.Graphene can be carried significantly
The performance of polymer is risen, therefore graphene composite coating turns into the important application research field of graphene.Graphene applies in conduction
The combination property of coating can be greatly improved in the coating systems such as material, anticorrosive paint, anti-flaming dope, such as reduces coating layer thickness,
Increase the adhesive force to base material, lift coating wearability, and make coating that there is green environmental protection.Especially in electrically-conducting paint, epoxy
In zinc-rich paint, water-based anticorrosive paint there is prominent performance to show, graphene will promote the new round industrial transformation of coating
Upgrading.
With the largely functionalization graphene containing oxy radical, it is strong with the adhesion of resin, high polymer material, and its suitable
Cooperation supporting material or functionalization material.The mode majority applied to coating of graphene is using graphene as feature at present
Filler is added, and it is the dispersion stabilization problem for how solving graphene, it is necessary to graphite thus to bring a key issue
Alkene is modified.Liu Lin etc. result of study shows:Chemically modified graphene and the surface of graphene oxide have abundant
Functional group(Hydroxyl, carboxyl, epoxy radicals), can realize that nanoscale disperses in polymer body, so as to effectively assign and
Improve the performance of polymer.Another application mode of graphene is to be prepared into graphene by the compound method of organic/inorganic
Composite, realize the stable dispersion of graphene and its performance of features.
At present both at home and abroad in graphene coating preparation, especially graphene dispersion, rotproofness and resistance to acids and bases etc.
Research achieved certain effect.Wherein wear a kind of graphene anticorrosive paint of the emerging invention of benevolence(Chinese invention patent application number
201610878263.1), increase the stability of graphene by carrying out secondary oxidation modification to graphite, be advantageous to maximum performance
The decay resistance of graphene in itself, the coating for making to prepare have excellent adhesive force, hardness and wearability and resistance to neutral salt
Mist corrosivity, but this method material requested is more, and preparation process is complicated, and cost is higher, and dispersiveness and resistance to acids and bases are bad.Separately
Outside, Qu Yanfa understands a kind of bi-component graphene anticorrosive paint(201510497999.X), graphene is added to anti-by this invention
In rotten coating, the thickness of coating paint film is greatly reduced;By the selection to each component, while antiseptic effect is improved, greatly
The big content for reducing zinc powder, overcomes zinc-rich paint to sacrifice anti-corrosion mode of the zinc powder as cost, greatly reduces and welding
Caused zinc oxide fog, environment-friendly, but this method complex technical process, cost is higher, at the same unresolved graphene with
The combination sex chromosome mosaicism of carrier.
It can be seen that cause its scattered uniformity, fine and close sexual intercourse there is the agglomeration because of graphene in itself in the prior art
Fork, easily overlap aggregation, at the same exist when graphene is equipped on general carrier with reference to it is insecure, easy to fall off, load factor is low
The problems such as.
The content of the invention
It is an object of the invention to provide a kind of high dispersive, the graphene coating of high corrosion resistant and preparation method, using focus on from
Beamlet carries out ise to silicon carbide ceramics particle, obtains carrier.Then in tube furnace, zinc powder is aoxidized into progress gas phase and sunk
Product, and chemical vapor-phase growing in-situ preparation graphene, graphene, in carrier hole, obtain acid and alkali-resistance and filled out with deposition of zinc oxide
Material.The filler is added in coating, can promote the fine dispersion of graphene, and the acid-proof alkaline of film is obviously improved, and can be solved
Certainly agglomeration of the graphene coating because of graphene obtained by conventional method in itself, causes its scattered uniformity, fine and close sex-intergrade,
Easily overlap aggregation, while avoids when graphene is equipped on general carrier and combine insecure, easy to fall off, load factor is low etc.
Problem, and then obtain high dispersive and high corrosion resistant performance.
Concrete technical scheme of the present invention is as follows:
A kind of high dispersive, the graphene coating of high corrosion resistant and preparation method, silicon carbide ceramics particle is entered using focused ion beam
Row ise, carrier is obtained, then in tube furnace, zinc powder oxidation is vapor-deposited, and chemical vapor-phase growing is in situ
Graphene is generated, graphene, in carrier hole, obtains acid and alkali-resistance filler with deposition of zinc oxide, and the filler is added in coating, can
Promote the fine dispersion of graphene, and the acid-proof alkaline of film is obviously improved.What is prepared comprises the following steps that:
(1)Ise is carried out to silicon carbide ceramics particle using focused ion beam, with Ga+Ion passes through control as ion gun
Ion beam current size processed, the pit of inverted trapezoidal is formed in silicon carbide, obtains the Carboround with high opening rate;
(2)By step(1)The Carboround of gained is placed on quartz plate, covers one layer of zinc powder, and cover one layer on its surface
Graphite powder, it is placed in quartz boat, quartz boat is placed in tube furnace center, then under nitrogen and oxygen flow, tube furnace is gradual
Heat up, after held for some time, made annealing treatment, then stop being passed through nitrogen and oxygen, be changed to be passed through methane gas progress
Reaction, stop ventilating methane gas after certain time, then room temperature is gradually cooling under argon gas and atmosphere of hydrogen, the graphene of generation
With deposition of zinc oxide in the etching hole of carborundum, the filler of acid and alkali-resistance is obtained;
(3)By step(2)The acid and alkali-resistance filler of gained is added in coating, is coated after well mixed, stone in obtained film
Black alkene is well dispersed, and the acid-proof alkaline of film be improved significantly.
Preferably, step(1)The silicon carbide ceramics particle is black silicon carbide, and proportion is 3.2~3.3g/cm2, particle diameter
For 20~30 μm.
Preferably, step(1)The ion beam current size is 1000~3000pA.
Preferably, step(1)The near coal-mine area of the pit is 4 μm of 2 μ m, 2 μm~4 μ m, and pit depth is 3~6 μ
m。
Preferably, step(2)The particle diameter of the zinc powder be 5~10 μm, its addition for Carboround quality 4~
8%。
Preferably, step(2)The quality of the covering graphite powder is the 15~25% of zinc powder quality, and particle diameter is 10~15 μm.
Preferably, step(2)The holding temperature is 800~1000 DEG C, and soaking time is 20~40min.
Preferably, step(2)The time of the annealing is 20~30min.
Preferably, step(2)The reaction time being passed through after methane gas is 15~20min.
Preferably, step(2)The cooling velocity is 0.5~1 DEG C/s.
Preferably, step(3)The addition mass ratio of the acid and alkali-resistance filler is 2~4%.
The present invention also provides a kind of high dispersive being prepared using above-mentioned preparation method, the graphene coating of high corrosion resistant.
Focused ion beam is a kind of new technology for being combined microanalysis with micro Process.Ise is by high energy Ga+
Ions Bombardment specimen surface sputters sample material and realizes etching.The particle being sputtered out has certain energy, can hit
Etching surface, a part are deposited to specimen surface again, and also some particle is deposited to pit after being elastically scattered again
Inner surface.The process that it is etched is as follows:When starting etching, redeposition mainly appears on pit edge, and thickness is smaller.With quarter
Erosion gradually deeply, start instantaneous redeposition occur inside pit, redeposition now is distributed mainly on the inner side of crater wall, few portion
Redeposition is in hole bottom after the bounce-back by crater wall for gradation, and based on cheating in the middle part of bottom.Simultaneously as the deposition at pit edge
Material blocks ion beam, ion beam can not be etched the deposition region of crater wall bottom, and the inclination angle of crater wall gradually forms, and promotes to lose
The cross sectional shape in hole develops to an inverted trapezoidal., can be on its surface after silicon carbide ceramics particle is used into focused-ion-beam lithography
Many pits are formed, improve specific surface area, and obtain higher percent opening, are used as the carrier of graphene and zinc oxide,
Load factor can be significantly improved, and is firmly combined with, it is difficult for drop-off.
Graphene has special laminar structured, can be used as filler as flakey mica powder, aluminium powder, glass flake etc.
Applied in anticorrosive paint.Its laminar structured good physical shielding that is diffused with to water, oxygen and ion acts on, Ke Yizeng
Add the infiltration distance of corrosive medium in the coating, so as to reach corrosion proof function, be referred to as " labyrinth effect ".Its stable sp2It is miscellaneous
Physical barriers can be formed between matrix and active medium by changing structure, prevent the progress of scattering and permeating.Meanwhile graphene exists
Under hot conditions or with can be kept relative stability in corrosive environment, the protection painting for extreme environment can be developed
Material.And zinc oxide can neutralize acid, alkaline matter simultaneously, secondary anti-corrosion is carried out to the acid and alkali substance for penetrating into coating.Thus, use
Graphene, as anticorrosive packing, can play cooperative effect with zinc oxide.The method of the present invention is in-situ preparation graphene and oxidation
Zinc, and be vapor-deposited on Carboround, due to good fluidity of the ball type carrier in cold coating, graphite is improved indirectly
The dispersiveness of alkene, while prevent itself reuniting for graphene.
Graphene coating prepared by the present invention, the method with directly adding graphene and zinc oxide(Carborundum is not prepared
Carrier, not using chemical deposition)Compare, the indoor anticorrosive grade of film and outdoor anti-corrosion grade are as shown in table 1.Can
See:The method of the present invention can assign coating excellent acid-alkali-corrosive-resisting performance, be highly suitable for tight to acid-proof alkaline requirement
Severe field.
Table 1
The invention provides a kind of high dispersive, the graphene coating of high corrosion resistant and preparation method, and compared with prior art, it is protruded
The characteristics of and excellent effect be:
1. graphene coating prepared by the present invention, graphene dispersion is good, is not susceptible to reunite again, is advantageous to maintain it scattered
Uniformity and compactness.
2. graphene coating prepared by the present invention, graphene is equipped on Carboround with zinc oxide in a manner of chemical deposition
On, be firmly combined with, be difficult for drop-off, load factor it is high.
3. graphene coating prepared by the present invention, its internal graphene serves dual etch-proof work with zinc oxide
With assigning coating excellent acid-alkali-corrosive-resisting performance, be highly suitable for the field harsh to acid-proof alkaline requirement.
4. the preparation method of the present invention, production equipment is common, and technique is relatively simple, easy to operate, and product cost is high, matter
Amount is stable.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of high dispersive, the graphene coating of high corrosion resistant and preparation method, it is as follows that it prepares the detailed process of corrosion resistant coating:
It is 3.3g/cm to take proportion2, particle diameter be 20 μm of silicon carbide ceramics particle, sputtering quarter is carried out to it using focused ion beam
Erosion, with Ga+For ion as ion gun, ion beam current size is 3000pA, and the pit of inverted trapezoidal is formed in silicon carbide, near coal-mine
Area is 2 μm of 2 μ m, and pit depth is 6 μm, obtains the Carboround with high opening rate;The Carboround of gained is put
In covering 10kg zinc powders, and the graphite powder for being 15 μm in its surface covering 2kg particle diameters on quartz plate, the stone of half opening is subsequently placed in
Ying Zhouzhong.Then quartz boat is placed in tube furnace center, then under nitrogen and oxygen flow, tube furnace is gradually heating to 1000
DEG C, after being incubated 20min, annealing 20min is carried out, then stops nitrogen and oxygen, is passed through methane gas and is reacted,
Stop reaction after 20min, room temperature be gradually cooling to 1 DEG C/s speed under argon gas and atmosphere of hydrogen, the graphene of generation with
Deposition of zinc oxide obtains the filler of acid and alkali-resistance in the etching hole of carborundum;By the acid and alkali-resistance filler with 2% mass ratio
Add in coating, be coated after well mixed, graphene dispersion is good in obtained film, and the acid-proof alkaline of film obtains
To being obviously improved.
The graphene coating obtained to embodiment 1, the indoor anticorrosive grade of its film and outdoor anti-corrosion grade are tested, is obtained
Data it is as shown in table 2.
Embodiment 2
A kind of high dispersive, the graphene coating of high corrosion resistant and preparation method, it is as follows that it prepares the detailed process of corrosion resistant coating:
It is 3.2g/cm to take proportion2, particle diameter be 25 μm of silicon carbide ceramics particle, sputtering quarter is carried out to it using focused ion beam
Erosion, with Ga+For ion as ion gun, ion beam current size is 3000pA, and the pit of inverted trapezoidal is formed in silicon carbide, near coal-mine
Area is 4 μm of 4 μ m, and pit depth is 3 μm, obtains the Carboround with high opening rate;The Carboround of gained is put
In covering 10kg zinc powders, and the graphite powder for being 15 μm in its surface covering 2.5kg particle diameters on quartz plate, half opening is subsequently placed in
In quartz boat.Then quartz boat is placed in tube furnace center, then under nitrogen and oxygen flow, tube furnace is gradually heating to
800 DEG C, after being incubated 40min, annealing 30min is carried out, then stops nitrogen and oxygen, is passed through methane gas and is reacted,
Stop reaction after 20min, room temperature, the graphene of generation are gradually cooling to 0.5 DEG C/s speed under argon gas and atmosphere of hydrogen
With deposition of zinc oxide in the etching hole of carborundum, the filler of acid and alkali-resistance is obtained;By the acid and alkali-resistance filler with 2% mass ratio
Example is added in coating, is coated after well mixed, graphene dispersion is good in obtained film, and the acid-proof alkaline of film
Be improved significantly.
The graphene coating obtained to embodiment 2, the indoor anticorrosive grade of its film and outdoor anti-corrosion grade are tested, is obtained
Data it is as shown in table 2.
Embodiment 3
A kind of high dispersive, the graphene coating of high corrosion resistant and preparation method, it is as follows that it prepares the detailed process of corrosion resistant coating:
It is 3.2g/cm to take proportion2, particle diameter be 22 μm of silicon carbide ceramics particle, sputtering quarter is carried out to it using focused ion beam
Erosion, with Ga+For ion as ion gun, ion beam current size is 2000pA, and the pit of inverted trapezoidal is formed in silicon carbide, near coal-mine
Area is 3 μm of 3 μ m, and pit depth is 5 μm, obtains the Carboround with high opening rate;The Carboround of gained is put
In covering 10kg zinc powders, and the graphite powder for being 12 μm in its surface covering 1.5kg particle diameters on quartz plate, half opening is subsequently placed in
In quartz boat.Then quartz boat is placed in tube furnace center, then under nitrogen and oxygen flow, tube furnace is gradually heating to
900 DEG C, after being incubated 25min, annealing 25min is carried out, then stops nitrogen and oxygen, is passed through methane gas and is reacted,
Stop reaction after 18min, room temperature be gradually cooling to 1 DEG C/s speed under argon gas and atmosphere of hydrogen, the graphene of generation with
Deposition of zinc oxide obtains the filler of acid and alkali-resistance in the etching hole of carborundum;By the acid and alkali-resistance filler with 2% mass ratio
Add in coating, be coated after well mixed, graphene dispersion is good in obtained film, and the acid-proof alkaline of film obtains
To being obviously improved.
The graphene coating obtained to embodiment 3, the indoor anticorrosive grade of its film and outdoor anti-corrosion grade are tested, is obtained
Data it is as shown in table 2.
Embodiment 4
A kind of high dispersive, the graphene coating of high corrosion resistant and preparation method, it is as follows that it prepares the detailed process of corrosion resistant coating:
It is 3.3g/cm to take proportion2, particle diameter be 28 μm of silicon carbide ceramics particle, sputtering quarter is carried out to it using focused ion beam
Erosion, with Ga+For ion as ion gun, ion beam current size is 1500pA, and the pit of inverted trapezoidal is formed in silicon carbide, near coal-mine
Area is 4 μm of 4 μ m, and pit depth is 6 μm, obtains the Carboround with high opening rate;The Carboround of gained is put
In covering 10kg zinc powders, and the graphite powder for being 10 μm in its surface covering 1.2kg particle diameters on quartz plate, half opening is subsequently placed in
In quartz boat.Then quartz boat is placed in tube furnace center, then under nitrogen and oxygen flow, tube furnace is gradually heating to
1000 DEG C, after being incubated 20min, annealing 30min is carried out, then stops nitrogen and oxygen, is passed through methane gas and is reacted,
Stop reaction after 15min, room temperature be gradually cooling to 1 DEG C/s speed under argon gas and atmosphere of hydrogen, the graphene of generation with
Deposition of zinc oxide obtains the filler of acid and alkali-resistance in the etching hole of carborundum;By the acid and alkali-resistance filler with 4% mass ratio
Add in coating, be coated after well mixed, graphene dispersion is good in obtained film, and the acid-proof alkaline of film obtains
To being obviously improved.
The graphene coating obtained to embodiment 4, the indoor anticorrosive grade of its film and outdoor anti-corrosion grade are tested, is obtained
Data it is as shown in table 2.
Embodiment 5
A kind of high dispersive, the graphene coating of high corrosion resistant and preparation method, it is as follows that it prepares the detailed process of corrosion resistant coating:
It is 3.2g/cm to take proportion2, particle diameter be 25 μm of silicon carbide ceramics particle, sputtering quarter is carried out to it using focused ion beam
Erosion, with Ga+For ion as ion gun, ion beam current size is 2500pA, and the pit of inverted trapezoidal is formed in silicon carbide, near coal-mine
Area is 2 μm of 2 μ m, and pit depth is 4 μm, obtains the Carboround with high opening rate;The Carboround of gained is put
In covering 10kg zinc powders, and the graphite powder for being 12 μm in its surface covering 1.8kg particle diameters on quartz plate, half opening is subsequently placed in
In quartz boat.Then quartz boat is placed in tube furnace center, then under nitrogen and oxygen flow, tube furnace is gradually heating to
850 DEG C, after being incubated 35min, annealing 28min is carried out, then stops nitrogen and oxygen, is passed through methane gas and is reacted,
Stop reaction after 15min, room temperature, the graphene of generation are gradually cooling to 0.5 DEG C/s speed under argon gas and atmosphere of hydrogen
With deposition of zinc oxide in the etching hole of carborundum, the filler of acid and alkali-resistance is obtained;By the acid and alkali-resistance filler with 3% mass ratio
Example is added in coating, is coated after well mixed, graphene dispersion is good in obtained film, and the acid-proof alkaline of film
Be improved significantly.
The graphene coating obtained to embodiment 5, the indoor anticorrosive grade of its film and outdoor anti-corrosion grade are tested, is obtained
Data it is as shown in table 2.
Embodiment 6
A kind of high dispersive, the graphene coating of high corrosion resistant and preparation method, it is as follows that it prepares the detailed process of corrosion resistant coating:
It is 3.2g/cm to take proportion2, particle diameter be 30 μm of silicon carbide ceramics particle, sputtering quarter is carried out to it using focused ion beam
Erosion, with Ga+For ion as ion gun, ion beam current size is 3000pA, and the pit of inverted trapezoidal is formed in silicon carbide, near coal-mine
Area is 3 μm of 3 μ m, and pit depth is 6 μm, obtains the Carboround with high opening rate;The Carboround of gained is put
In covering 10kg zinc powders, and the graphite powder for being 10 μm in its surface covering 1.5kg particle diameters on quartz plate, half opening is subsequently placed in
In quartz boat.Then quartz boat is placed in tube furnace center, then under nitrogen and oxygen flow, tube furnace is gradually heating to
1000 DEG C, after being incubated 20min, annealing 20min is carried out, then stops nitrogen and oxygen, is passed through methane gas and is reacted,
Stop reaction after 15min, room temperature be gradually cooling to 1 DEG C/s speed under argon gas and atmosphere of hydrogen, the graphene of generation with
Deposition of zinc oxide obtains the filler of acid and alkali-resistance in the etching hole of carborundum;By the acid and alkali-resistance filler with 3% mass ratio
Add in coating, be coated after well mixed, graphene dispersion is good in obtained film, and the acid-proof alkaline of film obtains
To being obviously improved.
The graphene coating obtained to embodiment 6, the indoor anticorrosive grade of its film and outdoor anti-corrosion grade are tested, is obtained
Data it is as shown in table 2.
Comparative example 1
Carboround is not prepared, not using chemical deposition, directly the graphene of respective quality and zinc oxide is added and applied
In material, other preparation conditions are consistent with embodiment 6.
The graphene coating obtained to comparative example 1, the indoor anticorrosive grade of its film and outdoor anti-corrosion grade are tested, wherein
Indoor anticorrosive grade is divided into:Indoor anti-moderate corrosion type F1;Indoor resistant to strong corrosion type F2;Outdoor anti-corrosion grade is divided into:Open air is anti-
Light corrosion type W;Outdoor anti-moderate corrosion type WF1;Outdoor resistant to strong corrosion type WF2, obtained data are as shown in table 2.
Table 2