CN105778134B - A kind of graphene composite polymer film material and preparation method thereof - Google Patents
A kind of graphene composite polymer film material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of graphene composite polymer film materials, it is characterized by: it include the polymeric membrane containing multiple through holes and be grown in polymeric membrane surface and through hole hole wall graphene, the graphene is grown in the surface of polymeric membrane and the hole wall of through hole by way of liquid deposition, and the bond strength of the graphene and polymeric membrane is 1Mpa~20Mpa.The present invention also provides a kind of preparation methods of graphene composite polymer film material.
Description
Technical field
The invention belongs to a kind of radiating element and preparation method thereof more particularly to a kind of graphene of high thermal conductivity are compound
Macromolecule member material and preparation method thereof.
Background technique
Heat Conduction Material has in national defense industry and national economy every field to be widely applied very much.With industrial production and section
The rapid development of technology, people propose update, higher requirement to Heat Conduction Material, in addition to thermal conductivity, it is desirable to which material has
Excellent comprehensive performance is for example light, workability, excellent in mechanical performance, resistant to chemical etching etc..High molecular material has light, resistance to
Chemical attack, easy processing molding, the excellent feature such as electrical insulation capability is excellent, mechanics and anti-fatigue performance are excellent.But macromolecule
Material is insulator, and thermal conductivity is extremely low, greatly limits it in the application in thermally conductive field.
In recent years, high development of information industry, such as high heat dissipation interface material widely used in electric appliance, microelectronic field
Material and encapsulating material, electromagnetic shielding, heat pipe, integrated circuit, cover copper at the widely used power tube of electronic information field, integrated package
The components such as substrate.Application of the high molecular material on these high-end information product accessories will be towards high power, high density
Change, is highly integrated, the directions such as rapid heat dissipation are developed, this development for high thermal conductivity high molecular material in new field provides bigger
Stage.
Currently, the thermal conductivity for improving high molecular material is mainly the filler by adding into matrix with high-termal conductivity
Method prepares filled-type polymer composite.Common filler has, and metal such as Au, Ag, Cu, Al, Mg etc., metal oxide is such as
A12O3, MgO, BeO, ZnO, NiO etc., metal nitride such as AlN, Si3N4, BN etc. and other nonmetallic materials such as graphite, charcoal
Black, carbon nanotube etc..Beneficial little Su etc. (please referring to document: Polymer Testing, 2004,23:797-801) is filled out with AlN particle
Polyimides is filled, is found when filling rate reaches 32.78%, thermal conductivity reaches 0.8W/mK.Lin Xiaodan, Zeng Xingrong etc. (are asked
Refering to document: plastics industry, 2006,34:65-67) by mixing polyphenylene sulfide (PPS) with magnesia through double screw extruder
Extruding pelletization is prepared for moulded heat-conductive insulated plastics, and when magnesia loading reaches 80%, thermal conductivity is up to 3.4W/mK.
Lin.Li etc. (please referring to document: Journal of electronic materials, 1994,23 (6): 557-564) has studied
The thermal coefficient of the PI composite material of AlN and SiC filling, when loading is 50%, the thermal conductivity of AlN/PI composite material from
0.128 is increased to 1.76W/mK；The thermal conductivity of SiC/PI system is increased to 1.26W/mK from 0.128.But presently, there are
The problem of be: 1. high thermal conductivity filler additive amount is difficult more than 50% in filled-type polymer composite；2. filled-type macromolecule
The thermal conductivity of composite material is high not enough.
In recent years, graphene was attracted wide attention as a kind of new material in the whole world.It is by carbon atom with
sp2What the monoatomic layer of hydridization connection was constituted, theoretic throat is only 0.35nm, is the most thin two-dimentional material found at present
Material.Graphene is the basic unit for constituting other carbon materials, can be warped into the fullerene of zero dimension, curls into one-dimensional CNTs
Or it is stacked to three-dimensional graphite.This special construction has contained abundant and peculiar physical phenomenon, and graphene is made to show to be permitted
Mostly excellent physicochemical properties.Referred to herein is its thermal property, it has as a kind of low-dimensional nano-carbon material
The up to pyroconductivity of 3000W/mK~6000W/mK is the best material of presently found heating conduction.Theoretically, exist
A small amount of graphene is added in macromolecule matrix can greatly improve high molecular thermal conductivity.But grapheme material also has not
Foot place, is difficult to disperse in macromolecule matrix, and graphene is not in sprawl shape but reunion shape in macromolecule matrix, because
This can not play the characteristic of its high heat conductance.
Therefore, the graphene composite polymer film material for developing high heat conductance not only has great creativeness, for
Application of the high molecular material in thermally conductive field also has huge impetus.
Summary of the invention
The main object of the present invention is to provide a kind of graphene composite polymer film material and preparation method thereof, the graphene
Composite polymer film material not only thermal conductivity with higher, bond strength also with higher, be applied to integrated circuit,
In the radiator of the electronic equipments such as electronic device, heat exchanger, LED, plays rapid cooling and ensure electronic component efficiently, surely
Fixed, long-life operation effect.
In order to achieve the goal above, the present invention proposes following technical scheme:
A kind of graphene composite polymer film material comprising the polymeric membrane containing multiple through holes and be grown in high score
The graphene of the hole wall of sub- film surface and through hole, the graphene are grown in the table of polymeric membrane by way of liquid deposition
The bond strength of the hole wall in face and through hole, the graphene and polymeric membrane is 1Mpa~20Mpa.
Wherein, the material of the polymeric membrane includes polyethylene (PE), polypropylene (PP), polystyrene (PS), poly- methyl
Methyl acrylate (PMMA), polyvinyl chloride (PVC), nylon (Nylon), polycarbonate (PC), polyurethane (PU), polytetrafluoroethylene (PTFE)
(PTFE) or polyethylene terephthalate (PET), the polymeric membrane with a thickness of 1 μm~1000 μm.
Wherein, the aperture of the through hole is 100nm~100 μm, hole density 101A/cm2~106A/cm2。
Wherein, the aperture of the through hole is 1 μm~50 μm, hole density 102A/cm2~104A/cm2。
Wherein, the graphene with a thickness of 0.01 μm~10 μm.
Wherein, the graphene is basically parallel to the surface of polymeric membrane or the hole wall of through hole.
A kind of preparation method of graphene composite polymer film material comprising following steps: by graphene and dispersing agent
It is mixed to form graphene dispersing solution in a solvent；Polymeric membrane surface with multiple through holes is subjected to negative electrical charge processing；It will
It is immersed in the graphene dispersing solution by the polymeric membrane that negative electrical charge is handled, takes out, be dried to obtain after 1min~10min
The graphene composite polymer film material, the surface of the polymeric membrane and the hole wall of through hole are deposited with the graphite
Alkene.
Wherein, the graphene is pure graphene powder or graphene slurry.
Wherein, the dispersing agent is the oligomer of phenylamine for forming the mutual power of π-π between graphene and realizing combination.
Wherein, the oligomer of phenylamine includes aniline tripolymer, in six aggressiveness of Tetraaniline, aniline pentamer or aniline
One kind or combination.
Wherein, the mass percent of graphene is 0.1%~10% in the graphene dispersing solution.
The preparation method of graphene composite high-molecular film of the present invention, which has the advantage that through oligomer of phenylamine, divides
Scattered graphene obtains homogeneous and stable graphene dispersing solution, since oligomer of phenylamine is positively charged so that graphene dispersing solution also band
Positive electricity.It will be immersed in positively charged graphene dispersing solution through the processed polymeric membrane of negative electrical charge, make the positive and negative of polymeric membrane
The hole wall of two sides and through hole is adequately contacted with dispersion liquid holding, and graphene dispersing solution is made to be deposited on macromolecule well
The surface of film and the hole wall of through hole.This liquid phase deposition process is realized by electrostatic attraction, and addition binder is eliminated
The operation applied, and graphene is attached to polymeric membrane surface by the way that electrostatic attraction is more stable.
Graphene composite polymer film material of the present invention and preparation method thereof is also equipped with following advantages:
(1) there is excellent heat dissipation performance.Although the thermal conductivity of graphene is high, its heating conduction has each to different
Property, the i.e. thermal conductivity in graphene planes direction can achieve 6000W/mK, but its vertical direction thermal conductivity only have 5W/mK~
30W/m·K.The graphene of prior art preparation is to be laid in polymeric membrane surface, direction of heat flow perpendicular to graphene planes,
Cause final heat dissipation effect unsatisfactory.Graphene composite high-molecular film of the present invention, polymeric membrane two sides and hole wall have
Graphene layer.The graphene layer of bottom not only can by heat rapid dispersion that heat source transmits on the surface of graphene, but also can will
To heat be quickly transferred to polymeric membrane top graphene layer by investing the graphene layer of hole wall.It is transferred to the heat on top
It is quickly spread by graphene planes, realizes rapid cooling eventually by the mode of convection current and radiation.That is, the graphite
The thermal conductivity on the direction perpendicular to polymeric membrane surface can be improved in graphene in the through hole of alkene composite high-molecular film, thus
Substantially increase the overall thermal conductivity of graphene composite polymer film material.
(2) graphene layer and polymeric membrane bond strength are high.The graphene of prior art preparation is laid in high score due to it
Sub- film surface, there are interfacial stresses between the two, thus graphene layer is easy to cause to remove.The compound high score of graphene of the present invention
Sub- film, graphene therein are not placed only in two surfaces up and down of polymeric membrane, Er Qiefen under the action of electrostatic attraction
It is distributed in the hole wall of through hole, this is distributed in upper and lower surface and the graphene of hole wall is connected and forms layer structure, by high score
Sub- film is clipped in the middle and entangles firm, to greatly improve the bond strength of graphene and polymeric membrane.In addition, passing through Electrostatic Absorption
The graphene composite high-molecular film that method is prepared, attachment stability of the graphene on polymeric membrane is strong, and bond strength is high.
(3) simple process, preparation cost are low.The prior art generally uses the method for chemical vapor deposition (CVD) in high score
Sub- film surface grows graphene, however this method needs high growth apparatus, and growth time is longer, and growth conditions is more demanding
(high temperature, high vacuum), and it is difficult on-line continuous growth.And the present invention is prepared graphene by the method for Electrostatic Absorption and answered
Close macromolecule member material, this method does not have a particular/special requirement to growth conditions, growth apparatus and substrate, growth time it is short (1min~
10min), and it can be grown with on-line continuous, to greatly improve production efficiency.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of graphene composite polymer film material of the present invention.
Wherein, 1 polymeric membrane is indicated；2 indicate through hole；3 indicate graphene layer.
Specific embodiment
Graphene composite polymer film material provided by the invention and preparation method thereof is made into one below with reference to attached drawing
Walk explanation.
Substance provided by the present invention can be synthesized by marketable material or traditional chemical transform mode.
Other aspects of the present invention are apparent to those skilled in the art due to this disclosure
's.
Below in conjunction with specific embodiment, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Unless otherwise defined or described herein, all professional and scientific terms used herein and the skilled people of art technology
Meaning known to member is identical.Furthermore any method similar to or equal to what is recorded and material all can be applied to the present invention
In method.
Referring to Fig. 1, the present invention provides a kind of graphene composite polymer film material, can be obtained by following preparation method
It arrives.The preparation method comprises the following steps:
(1) polymeric membrane 1 is subjected to surface cleaning processing, treatment process includes: that oil removing, pickling, washing, alcohol are washed, dried；
Wherein, the polymeric membrane 1 with a thickness of 1 μm~1000 μm.Preferably, the polymeric membrane 1 with a thickness of 10 μ
M~100 μm.
(2) polymeric membrane 1 after cleaning is subjected to aperture processing, aperture mode includes laser boring, plasma punching, machine
Tool drilling, chemical etching hole etc., obtain multiple through holes 2；
Wherein, the aperture of the through hole 2 is 100nm~100 μm, hole density 101A/cm2~106A/cm2.In order to
Make substrate heat dissipation more evenly, it is preferred that the aperture of the through hole 2 is 1 μm~50 μm, hole density 102A/cm2~104A/
cm2；
(3) negative electrical charge processing will be carried out with the polymeric membrane of multiple through holes；
Wherein, the surface of polymeric membrane can be made with negative electrical charge by the methods of Corona discharge Treatment.
(4) graphene and dispersing agent are mixed to form graphene dispersing solution in a solvent；
Specifically, graphene, dispersing agent and solvent are carried out by means such as high-speed stirred, ultrasound, ball milling and/or sand millings
Dispersion, obtains homogeneous and stable graphene dispersing solution.The dispersing agent is oligomer of phenylamine.The oligomer of phenylamine has good
Good dissolubility, dissolves in the solvent.The oligomer of phenylamine includes that aniline tripolymer, Tetraaniline, aniline five are poly-
One of six aggressiveness of body or aniline or combination.The oligomer of phenylamine can form π-π interaction force and reality between graphene
Now in conjunction with.Specifically, since the phenyl ring in the oligomer of phenylamine is due to close with graphene-structured, thus the aniline is oligomeric
Object can form pi-pi bond between graphene and realize and mix with graphene uniform.It should be pointed out that using oligomer of phenylamine with
Pi-pi bond is formed between graphene, this mode is different from grafting modification, the structure of graphene itself is not destroyed,
Different from the macromolecule of physical coated graphite alkene, the performance of graphene is not sacrificed.That is, passing through oligomer of phenylamine
Modification graphene only makes the dispersibility of graphene and stability more preferable, and does not destroy the structure of graphene, does not also drop
The low original performance of graphene.
The solvent can be deionized water, ethyl alcohol, acetone, isopropanol, butanol, ethyl acetate, toluene, chloroform, dimethyl
One of formamide, dimethyl sulfoxide dichloroethanes or combination.The mass percent of graphene in the graphene dispersing solution
(i.e. solid content) is 0.1%~10%.
(4) it will immerse in the graphene dispersing solution by the polymeric membrane of negative electrical charge processing, taken after 1min~10min
Out, drying obtains the graphene composite high-molecular film.The surface of the polymeric membrane and the hole wall of through hole are deposited with stone
Black alkene.Since oligomer of phenylamine is positively charged so that graphene dispersing solution is also positively charged, and the surface of polymeric membrane is negatively charged, the two
By strong electrostatic attraction, graphene is realized in the adventitious deposit on polymeric membrane surface, to obtain the compound high score of graphene
Sub- membrane material.
This is deposited on the surface of polymeric membrane and the graphene of the hole wall of through hole is connected to form layer structure, and incite somebody to action
Polymeric membrane is clipped in the middle and entangles firm.The graphene layer 3 is made of the pure graphene of multilayer.The graphene layer 3 covers institute
State the surface of polymeric membrane 1 and the hole wall of through hole 2.The number of plies of graphene is 1 layer~100 layers in the graphene layer 3.It is described
Graphene layer 3 with a thickness of 0.01 μm~10 μm.The thermal conductivity of obtained graphene composite high-molecular film be 20W/mK~
The bond strength of 500W/mK, graphene and polymeric membrane 1 is 1Mpa~20Mpa.The graphene composite polymer film material
It is applied in the radiator of integrated circuit, electronic device, heat exchanger or LED as heat dissipation element.
Compared to the prior art, the preparation method of graphene composite polymer film material of the present invention has following excellent
Point: homogeneous and stable graphene dispersing solution is obtained come dispersed graphite alkene by oligomer of phenylamine, just due to oligomer of phenylamine band
Electricity makes graphene dispersing solution also positively charged.Positively charged graphene dispersion will be immersed in through the processed polymeric membrane of negative electrical charge
In liquid, the hole wall of the tow sides and through hole that make polymeric membrane is adequately contacted with dispersion liquid holding, makes graphene point
Dispersion liquid is deposited on the surface of polymeric membrane and the hole wall of through hole well.This liquid phase deposition process is to pass through electrostatic attraction
It realizes, eliminates and the operation that binder is applied is added, and graphene is attached to high score by the way that electrostatic attraction is more stable
Sub- film surface.
Graphene composite polymer film material of the present invention and preparation method thereof is also equipped with following advantages:
(1) there is excellent heat dissipation performance.Although the thermal conductivity of graphene is high, its heating conduction has each to different
Property, the i.e. thermal conductivity in graphene planes direction can achieve 6000W/mK, but its vertical direction thermal conductivity only have 5W/mK~
30W/m·K.The graphene of prior art preparation is to be laid in polymeric membrane surface, direction of heat flow perpendicular to graphene planes,
Cause final heat dissipation effect unsatisfactory.Graphene composite high-molecular film of the present invention, polymeric membrane two sides and hole wall have
Graphene layer.The graphene layer of bottom not only can by heat rapid dispersion that heat source transmits on the surface of graphene, but also can will
To heat be quickly transferred to polymeric membrane top graphene layer by investing the graphene layer of hole wall.It is transferred to the heat on top
It is quickly spread by graphene planes, realizes rapid cooling eventually by the mode of convection current and radiation.That is, the graphite
The thermal conductivity on the direction perpendicular to polymeric membrane surface can be improved in graphene in the through hole of alkene composite high-molecular film, thus
Substantially increase the overall thermal conductivity of graphene composite polymer film material.
(2) graphene layer and polymeric membrane bond strength are high.The graphene of prior art preparation is laid in high score due to it
Sub- film surface, there are interfacial stresses between the two, thus graphene layer is easy to cause to remove.The compound high score of graphene of the present invention
Sub- film, graphene therein are not placed only in two surfaces up and down of polymeric membrane, Er Qiefen under the action of electrostatic attraction
It is distributed in the hole wall of through hole, this is distributed in upper and lower surface and the graphene of hole wall is connected and forms layer structure, by high score
Sub- film is clipped in the middle and entangles firm, to greatly improve the bond strength of graphene and polymeric membrane.In addition, passing through Electrostatic Absorption
The graphene composite high-molecular film that method is prepared, attachment stability of the graphene on polymeric membrane is strong, and bond strength is high.
(3) simple process, preparation cost are low.The prior art generally uses the method for chemical vapor deposition (CVD) in high score
Sub- film surface grows graphene, however this method needs high growth apparatus, and growth time is longer, and growth conditions is more demanding
(high temperature, high vacuum), and it is difficult on-line continuous growth.And the present invention is prepared graphene by the method for Electrostatic Absorption and answered
Close macromolecule member material, this method does not have a particular/special requirement to growth conditions, growth apparatus and substrate, growth time it is short (1min~
10min), and it can be grown with on-line continuous, to greatly improve production efficiency.
To further describe the present invention, here is the preparation method of the graphene composite polymer film material, in difference
Specific embodiment under parameter:
Embodiment 1:
100g graphene, 5g aniline tripolymer and 900g water are weighed, is uniformly mixed under high velocity agitation and is formed solid content and be
10% graphene dispersing solution.Selection aperture is 100 μm, hole density is 2000/cm2, with a thickness of 35 μm of porous PE films, and
It is started the cleaning processing and negative electrical charge is handled.Then the graphene will be immersed in by the porous PE film of negative electrical charge processing
It in dispersion liquid, is taken out after 1min, the compound PE film of graphene obtained by drying.Graphite is formed on the surface of PE film and the hole wall of through hole
Alkene layer, the graphene layer with a thickness of 1 μm.
PE film compound to the graphene is tested for the property.Specifically, being measured by heat reflection method film coefficient of heat transfer
Instrument (model Nano TR, German NETZSCH company) measures its thermal conductivity；By pulling open method adhesion-force tester (model
PosiTest AT, DeFelsko company of the U.S.) measure the bond strength of graphene and polymeric membrane.
Test result are as follows: the thermal conductivity of the compound PE film of graphene is 500W/mK, and the combination of graphene and PE film is strong
Degree is 10Mpa.
Embodiment 2:
10g graphene, 3g Tetraaniline and 990g ethyl alcohol are weighed, is uniformly mixed under high velocity agitation and is formed solid content and be
1% graphene dispersing solution.Choose aperture be 10 μm, hole density 104A/cm2, with a thickness of 5 μm of porous PP films, and to it
It starts the cleaning processing and negative electrical charge is handled.Then the graphene dispersion will be immersed in by the porous PP film of negative electrical charge processing
It in liquid, is taken out after 5min, the compound PP film of graphene obtained by drying.Graphene is formed on the surface of PP film and the hole wall of through hole
Layer, the graphene layer with a thickness of 0.5 μm.
PP film compound to the graphene is tested for the property.Test method is the same as embodiment 1.Test result are as follows: the stone
The thermal conductivity of the black compound PP film of alkene is 200W/mK, and the bond strength of graphene and PP film is 20Mpa.
Embodiment 3:
5g graphene, 2g aniline pentamer and 995g acetone are weighed, is uniformly mixed under high velocity agitation and is formed solid content and be
5 ‰ graphene dispersing solution.Choose aperture be 1 μm, hole density 105A/cm2, with a thickness of 100 μm of porous PU films, and to it
It starts the cleaning processing and negative electrical charge is handled.Then the graphene dispersion will be immersed in by the porous PU film of negative electrical charge processing
It in liquid, is taken out after 2min, the compound PU film of graphene obtained by drying.Graphene is formed on the surface of PU film and the hole wall of through hole
Layer, the graphene layer with a thickness of 0.1 μm.
PU film compound to the graphene is tested for the property.Test method is the same as embodiment 1.Test result are as follows: the stone
The thermal conductivity of the black compound PU film of alkene is 100W/mK, and the bond strength of graphene and PU film is 5Mpa.
Embodiment 4:
2g graphene, six aggressiveness of 2g aniline and 998g tetrahydrofuran are weighed, formation is uniformly mixed under high velocity agitation and contains admittedly
The graphene dispersing solution that amount is 2 ‰.Choose aperture be 50 μm, hole density 102A/cm2, with a thickness of 500 μm of porous PET films,
And it is started the cleaning processing and negative electrical charge processing.Then above-mentioned stone will be immersed in by the porous PET film of negative electrical charge processing
It in black alkene dispersion liquid, is taken out after 10min, the compound PET film of graphene obtained by drying.In the surface of PET film and the hole wall of through hole
Formed graphene layer, the graphene layer with a thickness of 0.3 μm.
The compound PET film of the graphene is tested for the property.Test method is the same as embodiment 1.Test result are as follows: the stone
The thermal conductivity of the black compound PET film of alkene is 20W/mK, and the bond strength of graphene and PET film is 2Mpa.
Embodiment 5:
1g graphene, 1g aniline tripolymer, 1g Tetraaniline and 999g toluene are weighed, is uniformly mixed under high velocity agitation
Form the graphene dispersing solution that solid content is 1 ‰.Choose aperture be 5 μm, hole density 103A/cm2, it is more with a thickness of 200 μm
Hole nylon membrane, and it is started the cleaning processing and negative electrical charge processing.Then it will be soaked by the porous nylon membrane of negative electrical charge processing
Enter into the graphene dispersing solution, is taken out after 8min, graphene composite nylon film obtained by drying.Nylon membrane surface and pass through
The hole wall of perforation forms graphene layer, the graphene layer with a thickness of 0.2 μm.
The graphene composite nylon film is tested for the property.Test method is the same as embodiment 1.Test result are as follows: described
The thermal conductivity of graphene composite nylon film is 50W/mK, and the bond strength of graphene and nylon membrane is 1Mpa.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.To these embodiments
A variety of modifications are it will be apparent that the general principles defined herein can be not for those skilled in the art
It is realized in other embodiments in the case where being detached from the spirit or scope of the present invention.Therefore, the present invention is not intended to be limited to this
These embodiments shown in text, and it is to fit to the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410815993.8A CN105778134B (en) | 2014-12-24 | 2014-12-24 | A kind of graphene composite polymer film material and preparation method thereof |
| TW104139658A TWI602611B (en) | 2014-12-02 | 2015-11-27 | Graphene dispersant and its application |
| EP15865917.7A EP3228592A4 (en) | 2014-12-02 | 2015-11-27 | DISPERSANT OF GRAPHENE AND ITS APPLICATION |
| PCT/CN2015/095742 WO2016086796A1 (en) | 2014-12-02 | 2015-11-27 | Graphene dispersant and application thereof |
| US15/607,552 US10696790B2 (en) | 2014-12-02 | 2017-05-29 | Graphene dispersant and application thereof |
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| CN109096750A (en) * | 2018-07-18 | 2018-12-28 | 桐城市明丽碳化硼制品有限公司 | A kind of graphene film and preparation method thereof |
| CN110743766A (en) * | 2019-11-08 | 2020-02-04 | 江苏科盾检测技术有限公司 | Natural gas pipeline corrosion prevention method |
| CN111393950B (en) * | 2020-04-22 | 2021-06-25 | 中国科学院山西煤炭化学研究所 | A kind of graphene anti-corrosion primer for heat exchanger in marine environment and preparation method thereof |
| CN112467418B (en) * | 2020-10-19 | 2021-06-22 | 南京盟瑞自动化有限公司 | Radio frequency connector with lightning protection function |
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