CN107828309A - Dispersion that a kind of graphene anticorrosive paint uses and preparation method thereof - Google Patents
Dispersion that a kind of graphene anticorrosive paint uses and preparation method thereof Download PDFInfo
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- CN107828309A CN107828309A CN201711065003.3A CN201711065003A CN107828309A CN 107828309 A CN107828309 A CN 107828309A CN 201711065003 A CN201711065003 A CN 201711065003A CN 107828309 A CN107828309 A CN 107828309A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides dispersion that a kind of graphene anticorrosive paint uses and preparation method thereof, and the dispersion that graphene anticorrosive paint uses is according to percent by weight：The component includes 20%~50% epoxy resin, 10%~20% graphene, 0.5%~3% dispersant, 0.5%~3% auxiliary agent, 15%~30% zinc powder.Graphene anticorrosive paint uses in the present invention dispersion simple process, stable storing, it can be applicable in various types of anticorrosive paints the excellent performances such as adhesive force, pliability, wearability and the salt fog resistance improved on metal substrate and protrude.
Description
Technical field
The present invention relates to anticorrosive paint field, especially provides dispersion and its preparation that a kind of graphene anticorrosive paint uses
Method.
Background technology
Since Univ Manchester UK AndreGeim in 2004 and KonstantinNovoselov successfully utilizes adhesive tape
The mode for peeling off graphite obtains single-layer graphene (graphene), and since the Nobel prize for physics of acquisition 2010, graphene
Electric conductivity, thermal conductivity, the various excellent properties such as chemical resistance i.e. constantly by industry by applied to different fields.Graphene is main
The two dimensional crystal structure of hexagonal honeycomb arrangement, its thickness only 0.335nm, that is, only one carbon are made up of sp2 hybridized orbitals
The size of atomic diameter, graphene are materials most thin and most hard at present, and mechanical strength can be far above hundred times of steel, and compare
The weight but only about a quarter of steel.In addition, graphene has excellent impenetrability and high-specific surface area, these characteristics can
Effectively extend the path of aqueous vapor and oxygen penetration polymer base material, reduce oxygen and moisture permeability, thus can apply to prevent
Etching ground.
CN104877402A discloses a kind of preparation method of graphene oxide anticorrosive paint.Add graphene oxide into
In anticorrosive paint, suitable component ratio is selected, while reduces the content of zinc powder, is advantageous to improve antiseptic property.
CN104371537A discloses a kind of preparation method of graphene oxide composite anticorrosion coating.By graphene oxide and
V_2O_5 thin films powder, montmorillonite mix with aniline monomer, then add DBSA, add persulfuric acid
Ammonium makes aniline that polymerisation occur, and is prepared into composite granule as raw material, is doped in anticorrosive paint, prepare particle diameter be 20~
80 μm of anticorrosive paint.
CN102604533A discloses a kind of anticorrosive paint and preparation method based on polyaniline and graphene composite material.
It is made up of in terms of weight fraction following components：Film forming matter 20~90；Polyaniline and graphene composite material 0.1~20；Pigment 1
~10；Filler 1~10；Anti-sagging agent 0.1~3；Dispersant 0.1~4；Levelling agent 0.01~2；Defoamer 0.01~2；Solvent 1
~50.Because radius-thickness ratio is high, pliability can provide well excellent physical preservation for the graphene in coating obtained by the invention
Effect, and the polyaniline for being supported on graphenic surface can provide electrochemical anti-corrosive effect, the synergy mechanism of the two causes
The coating has excellent metal erosion barrier propterty.The anticorrosive paint of the present invention, it is possible to achieve the passivation of metal base is eased up
Erosion, while the use of the heavy metals such as the chromium that can cause environmental pollution is avoided, and also preparation is simple, cost is low, is easy to industry
Change batch production.
A kind of Zinc-rich epoxy anticorrosion paints of CN103173095A, the coating include the first component of energy film-forming and contained
The second component of curing agent；Wherein, first component includes following component by mass percentage：0.1~5wt% of graphene；Zinc powder 0~
35wt%；30~70wt% of filler；Solid content is 54% 10~20wt% of epoxy resin；10~20wt% of solvent；Wherein, stone
The weight/mass percentage composition sum of black alkene, zinc powder and filler is 60~80wt%.By the selection to each component, anti-corrosion effect is being improved
While fruit, the content of zinc powder is greatly reduced, zinc-rich paint is overcome to sacrifice anti-corrosion mode of the zinc powder as cost, subtracts significantly
Lack in zinc oxide fog caused by welding, it is environment-friendly.
However, most normal problems faced is in practical application, graphene be easy to aggregation, storehouse and lump, that is, not
It is easily dispersed, the graphene platelet unevenly phenomenon of storehouse each other how is prevented, to obtain high uniformity and the number of plies is few
Graphene powder, always be industrial circle most need solve technical bottleneck.
The content of the invention
The purpose of the present invention is the deficiency being directed in existing anticorrosive paint technique and performance, and directly uses graphene powder
Yi Yin disperses bad and leads to not the performance for playing graphene, and researching and developing one kind with this reason prepares the use of graphene anticorrosive paint
Dispersion, the dispersion is easily uniformly dispersed in resin, adds using after being done according to the performance requirement of anticorrosive paint.
The technical scheme is that, there is provided the dispersion that a kind of graphene anticorrosive paint uses, it is characterised in that according to
Percent by weight：20%~50% epoxy resin, 10%~20% graphene, 0.5%~3% dispersant, 0.5%~
3% auxiliary agent, 15%~30% zinc powder, wherein each component percetage by weight sum are 100%.
Further, epoxy resin is made up of the epoxy resin that epoxide number is 0.09~0.114.
Further, graphene film is the graphene film of few layer or the graphene film of multilayer, and its graphene purity is greater than
95wt%, thickness is 1nm to 20nm section, and plane lateral dimension is in 1 μm to 100 μm of section.The graphene is
It is prepared by graphite through physical method, the physical method includes but is not limited to, and micromechanics stripping method, liquid phase or gas phase are direct
Stripping method or thermal decomposition SiC methods etc..
Further, the anti-settling agent includes but is not limited to modified urea solution, and the anti-settling agent described in it is preferably finished by Germany
Gram chemical product BYK-410, BYK-420 etc. are formed.
Further, the levelling agent includes but is not limited to silicone levelling agent etc., the levelling agent described in it preferably by
The product BYK-310 of German Bi Ke chemistry is formed.
Further, the defoamer includes but is not limited to organic silicon defoamer etc., such as the product that extra large name Si De is modest
Defom 6500 is formed.
Further, the dispersion that described graphene anticorrosive paint uses, the mixed solvent described in it is by mass ratio
For 7:3 dimethylbenzene forms with n-butanol.
Further, the dispersant is with polynary anchoring group with compatible with graphene and epoxy resin solution
Hyperbranched poly ester copolymer described in dispersant be with compatible with graphene and epoxy resin solution with polynary anchoring base
The hyperbranched poly ester copolymer of group, the dispersant is adsorbed in graphenic surface by the anchoring group in structure, via phase
Hold segment be scattered in resin or grinding circle it is straight in, reach stable and protect the effect of graphene；Dispersant described in it is by extra large name
The modest product NUOSPERSE FX 9086 of this moral, NUOSPERSE FX 9360, NUOSPERSE FX 9200, NUOSPERSE
FA 196, NUOSPERSE FX 600 etc. are formed.The dispersant is adsorbed in graphene table by the anchoring group in structure
Face, it is being scattered in via compatibility segment in resin or abrasive media, is reaching stable and protect the effect of graphene.
Further, the anticorrosive paint that the dispersion that described graphene anticorrosive paint uses is made, it is characterised in that
0 grade of the paint adhesion；Resistance to positive and negative impact>50cm；Pliability<3mm；Salt spray resistance>1000h.
The present invention further provides the preparation method for the dispersion that graphene anticorrosive paint uses, and it includes following step
Suddenly：
Step a：The desired amount of epoxy resin, dispersant are weighed, adds part mixed solvent, is mixed；
Step b：The graphene of required surplus and zinc powder are added in high shear mixing dispersion machine, control temperature 20~30
DEG C, rotating speed 1500rpm~2000rpm, shear 20~30min；
Step c：The obtained mixtures of step b are transferred in sand mill, are ground to fineness<30μm；
Step d：The mixture that step c is obtained adds the desired amount of auxiliary agent, controls rotating speed 300rpm~600rpm, shearing
Finished product is obtained after 20~30min.
It is solid-state under the epoxy resin normal temperature selected by dispersion that graphene anticorrosive paint prepared by the present invention uses, makes
Used time need to be dissolved in the mixed solvent in advance.The resin epoxy equivalent weight is higher, and the paint film crosslink density of formation is big, has preferable
The anti-medium osmosis performance of paint film, and it is splendid with graphene compatibility, therefore preferred epoxy of the present invention is as graphene anti-corrosion
The matrix resin for the dispersion that coating uses.
The few layer graphene piece or multilayer that the graphene used in the present invention is preferably prepared by graphite through physical method
Graphene film, its graphene purity are greater than 95wt%, and thickness is 1nm to 20nm section, and plane lateral dimension is at 1 μm
To 100 μm of section.Found by studying, using piece footpath in 20~25 μm, graphene of the number of plies 10~15, resulting painting
Material is optimal with optimal combination property, and particle diameter is too small to cause graphene dispersion difficult, and paint stability is deteriorated；Particle diameter mistake
Greatly, then cause coating to disperse bad appearance of coat coarse, and coating performance can be reduced.
The dilute feature of graphite that the present invention is prepared for physical method, from the tool compatible with decentralized medium resin solution
There is the hyperbranched poly ester copolymer of polynary anchoring group, the dispersant is adsorbed in graphene table by the anchoring group in structure
Face, it is being scattered in via compatibility segment in resin or abrasive media, is reaching stable and protect the effect of graphene.
The compounded mix for the dispersion that the present invention is used from zinc powder as graphene anticorrosive paint.Zinc powder is because of its high potential
Characteristic there is at a relatively high corrosion resistance in the coating, when coating run into corrosion factor invasion and attack when, zinc powder and graphene are painting
Conductive layer is mutually connected in film, cathodic protection effect is played, so as to protect steel, iron ground.In addition, in the process of coating film forming
In, the layer structure of graphene can in resin it is overlapping it is arranged in parallel form fine and close impermeable layer, extend various corrosion
Medium is penetrated into the approach of protected surface of bottom material by coating surface.
The anticorrosive paint made by dispersion that graphene anticorrosive paint prepared by the present invention uses is compared to directly addition stone
Anticorrosive paint prepared by black alkene powder has following performance advantage：
1st, the dispersion that the present invention is used using high shear mixing dispersal mechanism for graphene anticorrosive paint, passes through high shear
Convection current disperses, and graphene can not only keep original structure, and be uniformly dispersed in the presence of dispersant in paint vehicle, and by
By graphene and the very big characteristic of zinc powder difference of specific gravity, cladding is completed in process of lapping；The method efficiently solves graphite
The problem of alkene is easily reunited in coating, is difficult scattered, prepared by favourable follow-up large-scale coating material production.
2nd, the dispersion that this graphene anticorrosive paint uses directly can be made an addition in anticorrosion paint formulation, and pole can effectively carry
The coating property is risen, it is convenient many to prepare coating relatively to add Graphene powder, and larger in coating can give play to graphene
Performance.
3rd, the equipment requirement of downstream coating material production producer is reduced, reduces cost of manufacture.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained on the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
[embodiment 1]
Step a：It is formulated by table 1 Suo Shi, by the epoxy resin of formula ratio, dispersant, adds part mixed solvent (mass ratio
For 7:3 dimethylbenzene and n-butanol) add in stirring container, it is dispersed with stirring under 300-600r/min rotating speed uniformly；
Step b：The graphene of required surplus and zinc powder are added in high shear mixing dispersion machine, control temperature 20-30
DEG C, rotating speed 1500rpm-2000rpm, shear 20-30min；
Step c：The obtained mixtures of step b are transferred in sand mill, are ground to fineness<30μm；
Step d：The mixture that step c is obtained adds the desired amount of levelling agent, defoamer, anti-settling agent, controls rotating speed
300rpm-600rpm, finished product is obtained after being dispersed with stirring 20-30min.The dispersion that measurement gained graphene anticorrosive paint uses is each
Item physical index, it is specific as shown in table 2.
[embodiment 2~4]
It is as shown in table 1 according to the preparation method of embodiment 1, the content of each component during adjustment is formulated, formula.
[comparative example 1]
According to the preparation method of embodiment 1, differ only in and be added without dispersant, formula is as shown in table 1.
The dispersion formula that each embodiment graphene anticorrosive paint of table 1 uses
The dispersion physical index that graphene anticorrosive paint prepared by 2 each embodiment of table uses
Its specific surface area of graphene is big, and oil absorption is high, has higher surface energy, and interaction force between layers
By force, preferable graphene performance is obtained, the average grain diameter after it is scattered is vital factor, and being shown through experimental result makes
With hyper-branched polyester copolymer dispersant, preferable dispersion particle diameter, significant raising slurry gloss of film degree and drop can not only be obtained
Low-viscosity, and the dispersion stabilization of graphene dispersion body can be greatly improved.
It can be found from table 2, comparative example 1 due to no added any dispersant, with zinc powder can not by the graphene in slurry
Effectively disperse and generate the phenomenon of reunion, therefore fineness is relative with viscosity higher；Two branched dispersing agents show similar grinding effect
Mill base viscosity profile is all suitable after rate and grinding, and dispersive agent ratio suggestion is using Graphene powder body weight as the upper limit in slurry
Optimal grinding efficiency and suitable slurry viscosity can be obtained, the same ground slurry that is formulated carries out thermmal storage stability test in 50
After being placed 7 days at DEG C observe mill base before and after outward appearance and settleability change, show that hyperbranched poly ester copolymer disperses from data
Agent is dispersed with preferable viscosity stability and slurry compared with commercially available product, therefore the formula of preferred embodiment 4 is as follow-up anti-
Rotten coating makes the dispersion that required graphene anticorrosive paint uses.
[embodiment 5]
1st, component A is prepared
Step a：It is formulated by table 3 Suo Shi, the epoxy resin, levelling agent, mixed solvent of A group of formula amounts is added into stirring container
In, stirred under 300-600r/min rotating speed to being uniformly dispersed；
Step b：Then the graphene of component A formula ratio is sequentially added, is continued under 800-1000r/min rotating speed
Stirring is equal to disperseing
Step c：The obtained mixtures of step b are added in grinder and are ground to fineness less than 30 microns, A groups are made
Part.
2nd, B component is prepared
It is 1 by weight by dimethylbenzene and n-butanol:1 mixed solvent being configured to, the solvent as B component.By the institute of table 3
Show formula, the curing agent of B component formula ratio and solvent are mixed successively, obtain B component.
[embodiment 6]
1st, component A is prepared
Step a：It is formulated by table 3 Suo Shi, the epoxy resin, levelling agent, mixed solvent of A group of formula amounts is added into stirring container
In, stirred under 300-600r/min rotating speed to being uniformly dispersed；
Step b：Then the dispersion (embodiment 4) that the graphene anticorrosive paint of component A formula ratio uses is sequentially added,
Continue stirring under 800-1000r/min rotating speed to being uniformly dispersed；
Step c：The obtained mixtures of step b are added in grinder and are ground to fineness less than 30 microns, A groups are made
Part.
2nd, B component is prepared
It is 1 by weight by dimethylbenzene and n-butanol:1 mixed solvent being configured to, the solvent as B component.By the institute of table 3
Show formula, the curing agent of B component formula ratio and solvent are mixed successively, obtain B component.
[embodiment 7]
1st, component A is prepared
Step a：It is formulated by table 3 Suo Shi, is formulated by table 3 Suo Shi, the epoxy resin of A group of formula amounts, levelling agent, mixing is molten
Agent is added in stirring container, is stirred under 300-600r/min rotating speed to being uniformly dispersed；
Step b：Then zinc powder, the graphene of component A formula ratio are sequentially added, under 800-1000r/min rotating speed after
It is continuous to be stirred to scattered equal
Step c：The obtained mixtures of step b are added in grinder and are ground to fineness less than 30 microns, A groups are made
Part.
2nd, B component is prepared
It is 1 by weight by dimethylbenzene and n-butanol:1 mixed solvent being configured to, the solvent as B component.By the institute of table 3
Show formula, the curing agent of B component formula ratio and solvent are mixed successively, obtain B component.
[embodiment 8]
1st, component A is prepared
Step a：It is formulated by table 3 Suo Shi, the epoxy resin, levelling agent, mixed solvent of A group of formula amounts is added into stirring container
In, stirred under 300-600r/min rotating speed to being uniformly dispersed；
Step b：Then the zinc powder of component A formula ratio is sequentially added, the dispersion (embodiment that graphene anticorrosive paint uses
4) stirring, is continued under 800-1000r/min rotating speed to being uniformly dispersed；
Step c：The obtained mixtures of step b are added in grinder and are ground to fineness less than 30 microns, A groups are made
Part.
2nd, B component is prepared
It is 1 by weight by dimethylbenzene and n-butanol:1 mixed solvent being configured to, the solvent as B component.By the institute of table 3
Show formula, the curing agent of B component formula ratio and solvent are mixed successively, obtain B component.
[comparative example 2]
1st, component A is prepared
It is formulated by table 3 Suo Shi, the epoxy resin, levelling agent, mixed solvent of A group of formula amounts is added in stirring container,
Stirred under 300-600r/min rotating speed to being uniformly dispersed；
2nd, B component is prepared
It is 1 by weight by dimethylbenzene and n-butanol:1 mixed solvent being configured to, the solvent as B component.By the institute of table 3
Show formula, the curing agent of B component formula ratio and solvent are mixed successively, obtain B component.
The formulation for coating material (parts by weight) of the dispersion used in 3 each embodiment of table using graphene anticorrosive paint
It is ripe after embodiment 5-8 and comparative example 2 scattered coating component A and B component are well mixed by equivalent proportioning
Change 15min, be sprayed on test sample plate surface, the model for spraying paint film is placed under constant-temperature constant-humidity environment after conserving 7 days, with reference to phase
Anticorrosive paint performance prepared by its combination property of pass standard testing, comparative example 2 and embodiment 5-8 is shown in Table 4.
Graphene anticorrosive paint combination property prepared by 4 each embodiment of table
| Comparative example 2 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Pencil hardness | 2B | H | 2H | H | 2H |
| Adhesive force (level) | 2 | 1 | 0 | 1 | 0 |
| Pliability (mm) | 4 | 3 | 2 | 5 | 4 |
| Impact resistance (cm) | 70 | 30 | 50 | 40 | 50 |
| Abrasion performance (mg) | 150 | 90 | 75 | 120 | 105 |
| Salt fog resistance (hr) | <200 | <500 | <600 | <950 | <1100 |
The dispersion that graphene anticorrosive paint prepared by the present invention uses can be found from the data of Experimental comparison, be made anti-
The performance of rotten coating is far above comparative example, and performance is more more excellent than the anticorrosive paint for directly adding graphene powder, in addition should
Dispersion simple process that graphene anticorrosive paint uses, stable storing, adhesive force is excellent on the grounds such as steel, iron, pliability
With the excellent in mechanical performance such as anti-wear performance, and barrier propterty is dashed forward under the extreme severe rugged environment such as high/low temperature, strong acid-base, high salinity
Go out.
Above is elaborating to a kind of dispersion used for graphene anticorrosive paint of the present invention and preparation method thereof,
It is used to help understand the present invention, but embodiments of the present invention and is not restricted to the described embodiments, it is any without departing from the present invention
Change, modification, replacement, combination, the simplification made under principle, should be equivalent substitute mode, be included in the guarantor of the present invention
Within the scope of shield.
Claims (9)
1. the dispersion that a kind of graphene anticorrosive paint uses, including following component：According to percent by weight：20%~
50% epoxy resin, 10%~20% graphene, 5%~15% dispersant, 0.5%~3% auxiliary agent, 15%-30% zinc powders.
2. the dispersion that graphene anticorrosive paint according to claim 1 uses, it is characterised in that：The epoxy resin by
The epoxy resin that epoxide number is 0.09~0.114 forms.
3. the dispersion that graphene anticorrosive paint according to claim 1 uses, it is characterised in that：The graphene is few
The graphene film of layer or the graphene film of multilayer, its graphene purity are greater than 95wt%, and thickness is 1nm to 20nm section, and
Plane lateral dimension is in 1 μm to 100 μm of section, and the graphene is to be prepared by graphite through physical method.
4. the dispersion that graphene anticorrosive paint according to claim 1 uses, it is characterised in that：Count in parts by weight,
It is mixed solvent that the adjuvant component, which includes 0.2%~1% levelling agent, 0.2%~1% defoamer, 0.2~1% anti-settling agent, surplus,.
5. the dispersion that graphene anticorrosive paint according to claim 4 uses, it is characterised in that：The anti-settling agent includes
Modified urea solution.
6. the dispersion that graphene anticorrosive paint according to claim 4 uses, it is characterised in that：The mixed solvent is
Mass ratio is 7:3 dimethylbenzene and n-butanol.
7. the dispersion that graphene anticorrosive paint according to claim 1 uses, it is characterised in that：The dispersant is tool
There is the hyperbranched poly ester copolymer with polynary anchoring group compatible with graphene and epoxy resin solution.
8. the dispersion that the graphene anticorrosive paint according to any one of claim 1~7 uses, it is characterised in that：By institute
The anticorrosive paint that the dispersion that the graphene anticorrosive paint stated uses is made, its adhesive force are 0 grade, resistance to positive and negative impact>50cm,
Pliability<3mm, salt spray resistance>1000h.
9. the preparation method for the dispersion that the graphene anticorrosive paint according to any one of claim 1~8 uses, its feature
It is, comprises the following steps：
Step a：The desired amount of epoxy resin, dispersant are weighed, adds part mixed solvent, is mixed；
Step b：The graphene of required surplus and zinc powder are added in high shear mixing dispersion machine, 20~30 °C of temperature of control,
Rotating speed 1500rpm~2000rpm, shear 20~30min；
Step c：The obtained mixtures of step b are transferred in sand mill, are ground to fineness<30μm；
Step d：The desired amount of auxiliary agent of mixture addition that step c is obtained, control rotating speed 300rpm~600rpm, shearing 20~
Finished product is obtained after 30min.
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Cited By (4)
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| CN108530969A (en) * | 2018-04-21 | 2018-09-14 | 杭州烯创科技有限公司 | Application in water-repellent paint graphene dispersion body, preparation method and color steel tile |
| CN109021621A (en) * | 2018-07-25 | 2018-12-18 | 广东好邦石墨烯新材料科技有限公司 | A kind of zinc powder of graphene modified, preparation method and its application in water-based anticorrosive paint |
| CN110028828A (en) * | 2019-04-03 | 2019-07-19 | 常州第六元素材料科技股份有限公司 | The graphene composite dry powder and preparation method of high solids content, epoxy zinc-enriched paint and preparation method |
| CN110183934A (en) * | 2019-05-30 | 2019-08-30 | 陈理抗 | A kind of wear-resisting type bi-component graphene anticorrosive paint |
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| CN110183934A (en) * | 2019-05-30 | 2019-08-30 | 陈理抗 | A kind of wear-resisting type bi-component graphene anticorrosive paint |
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