CN107217249A - Graphene silane filming agent and preparation method thereof - Google Patents
Graphene silane filming agent and preparation method thereof Download PDFInfo
- Publication number
- CN107217249A CN107217249A CN201710390309.XA CN201710390309A CN107217249A CN 107217249 A CN107217249 A CN 107217249A CN 201710390309 A CN201710390309 A CN 201710390309A CN 107217249 A CN107217249 A CN 107217249A
- Authority
- CN
- China
- Prior art keywords
- graphene
- silane
- filming agent
- agent according
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
Abstract
A kind of graphene silane filming agent, by percentage to the quality, is made up of following raw material:Modified graphene 0.08 0.18%;Silane coupler 0.6 1.1%;Adhesion promoter 0.3 0.8%;Complex compound 1.6 2.2%;Fluoride 0.8 1.0%;Surplus is water.There is good adhesive force between the graphene organosilan hybridized film and metal surface painting layer of graphene silane filming agent formation, and graphene organosilan hybridized film has good decay resistance.
Description
Technical field
The present invention relates to metal conditioner field, in particular, it is related to a kind of in metal surface formation nanoscale
The graphene silane filming agent of other chemical composition coating.
Background technology
Current metal surface pre-treatment largely uses phosphating process, with the continuous propulsion of energy-saving and emission-reduction, tradition
Phosphating process is withdrawn from the market constantly.The phosphate-free metals such as emerging zirconium system, zirconium titanium system, silane system, silane zirconium system are surface-treated
Agent, has captured rapidly market.But the properties of these without phosphorus conversion films are suitable with conventional phosphatizing film properties, without superiority,
The demand of the high anti-corrosion industry application such as ship can not be met.
Chinese patent CN200910034639.0 is related to a kind of phosphorus-free film forming agent, and its raw material is by with following percentage by weight
Component composition:0.5%~4% silane coupler, 0.5%~2% titanate coupling agent, 1%~10% fluorine zirconic acid or zirconates,
3%~5% alcohols solvent, 0.5%~2% hydrofluoric acid or fluoride, 1%~5% hydrogen peroxide, 0.5%~2% nitric acid or nitre
Hydrochlorate, and surplus deionized water or running water, the present invention have environmental protection, the spy of adhesive force and anti-corrosion capability can be improved
Point.The patent belongs to phosphate-free metal surface conditioning agent, and the properties of its film layer are suitable with conventional phosphatizing film properties, but film layer
Decay resistance and wet-hot aging performance etc. can not meet the demand of ship grade high anti-corrosion industry application.
Chinese patent CN201610762549.3 proposes a kind of nanometer silane graphene vitrification film, including following parts by weight
Each component:Film forming agent 3-5%, oxidant 2-4%, complexing agent 1-2%, coupling agent 1-3%, wetting agent 0.5-1.5%, graphene 2-
4%, surplus is water, wherein, the coupling agent includes silane coupler.The product of the present invention, it is without phosphorus, it is more environmentally-friendly, it is silane coupled
The addition of agent, enhances the corrosion resistance and adhesive force of film layer, and the addition of graphene, and the corrosion resistance of film layer is further carried
Height, and the fillibility in space is more preferable;Furthermore, the electric conductivity of graphene is most powerful, so in application electrostatic powder coating
During more preferable absorption powder coating.The consumption of coupling agent and graphene all reaches a few percent in the patent, and these unit prices are super
The too conference of high raw material usage causes reagent cost high.
Chinese patent CN 201610494271.6 discloses a kind of graphene-based film agent, consisting of:Nano-graphene
0.1-1 parts, 1-3 parts of graphene dispersion agent, 2-10 parts of fluoric-containing acid, fluorine-containing hydrochlorate 2-10 parts, 1-2 parts of silane coupler, complexing agent
2-5 parts, 0-2 parts of surface active agent, 70-95 parts of water.The present invention has the advantages that short film formation time, good film-forming property, environmental protection, this hair
Bright to form inoranic membrane in metal surface and have excellent lubricity, anticorrosive property, film layer is thin, and the inorganic nano film of formation has excellent
Good electric conductivity, greasy property and corrosion resistance, with higher corrosion resistance and salt fog time, so as to preferably improve
The decay resistance of metal base, and virgin metal surface impedance is not influenceed after film forming, it is more beneficial for the finishing of metal.The patent
Shortcoming one is that the consumption of nano-graphene and silane coupler in the patent is big, causes with high costs.Two be patent formation
Inoranic membrane has excellent lubricity, PASS can be caused not good, can cause graphene-based epithelium and metallic matrix or
Adhesive force is bad between graphene-based epithelium and paint, causes graphene-based epithelium or peeling paint.
Chinese patent CN201610569185.7 provides a kind of graphene metal conditioner, by weight percentage,
It is made up of following raw material:Na meters of Shi Mo Xi ﹑ 2-10% Fu Gao Suan ﹑ 2-10% Ning Meng Suan ﹑ 0.5-2.0% ethylenediamines of 0.003-0.030%
Tetraacethyl disodium, surplus is water.The graphene metal conditioner is applied to metal surface pre-treatment, can be looked unfamiliar in metal watch
It is nano level graphene nano composite membrane into thickness, with higher film layer, coating binding force and decay resistance, it is adaptable to
The Pretreatment Line of the industry metalworks such as Qi Che ﹑ Hang days Hang Kong ﹑ Jun Gong ﹑ Jia electricity ﹑ engineering machinery.Nano-graphene in the patent
Belong to film forming host with fluorine zirconic acid, citric acid belongs to complexing agent with disodium ethylene diamine tetraacetate, and no oxidant or attachment are made every effort to promote
Enter agent composition, there is that film formation time is longer, the phenomenon of poor-performing.
The content of the invention
An object of the present invention is to overcome the deficiencies in the prior art that there is provided a kind of graphene silane filming agent, this stone
The graphene of black alkene silane filming agent formation-have good attachment between organosilan hybridized film and metal surface painting layer
Power, and decay resistance.
The second object of the present invention is the preparation method for providing above-mentioned graphene silane filming agent.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of graphene silane filming agent, by percentage to the quality, is made up of following raw material:
Modified graphene 0.08-0.18%;
Silane coupler 0.6-1.1%;
Adhesion promoter 0.3-0.8%;
Complex compound 1.6-2.2%;
Fluoride 0.8-1.0%;
Surplus is water.
The preferred 0.10-0.15% of consumption of the modified graphene, modified graphene consumption is too low, and film layer porosity is big, dredges
Pine;Modified graphene consumption is too high, film layer and metallic matrix poor adhesive force.
Wherein modified graphene is the water-soluble graphene that surface carries hydroxyl, and wherein hydroxy radical content is 0.005-
0.012%。
The preparation method of the modified graphene is as follows:
1)Natural flake graphite is added in the concentrated sulfuric acid at 0-2 DEG C and stirs 2-3h;It is then slowly added into potassium peroxydisulfate and five oxygen
Change and 3-5h is stirred at two phosphorus, 20-25 DEG C, then be warming up at 40-45 DEG C and stir 24-48h, then slowly add water stirring 2-3h, then
Hydrogen peroxide is slowly added to, the suspension of glassy yellow particulate matter is obtained;The centrifugation of glassy yellow particulate matter is separated, after being eluted with water, 60-
12-24h is dried in vacuo at 65 DEG C, graphene oxide is obtained;
2)Add graphene oxide into thionyl chloride, return stirring 24-36 h at 80 DEG C, separation is then centrifuged for, through acetone
After cleaning, 12-18h is dried in vacuo at room temperature, graphene of the surface containing acid chloride groups is obtained;
3)Graphene of the surface containing acid chloride groups and 1,3- propane diamine are added separately in N, N '-dimethyl formamide, in nitrogen
Under gas shielded, 24-36h is stirred at 80 DEG C, N is then removed under reduced pressure, N '-dimethyl formamide, after washing with water, vacuum at room temperature
24-48h is dried, graphene of the surface with amino is obtained;
4)Graphene of the surface with amino and Cyanuric Chloride are added separately in tetrahydrofuran at 0-3 DEG C, stirring reaction 24-
After 36h, tetrahydrofuran is removed under reduced pressure, after being cleaned through ether, 12-24h is dried in vacuo at 10-15 DEG C, obtain surface containing triazine ring
Graphene;
5)By graphene of the surface containing triazine ring in N, N '-dimethylformamide after stirring and dissolving, in 5-10h at 40 DEG C
Inside it is slowly dropped in the N containing diatomic alcohol compounds, N '-dimethyl formamide solution, completion of dropping is anti-after 45 DEG C of constant temperature
12-48 h are answered, then are warming up to 90 DEG C of isothermal reaction 24-60h, solvent is removed under reduced pressure, after being cleaned through distilled water, vacuum is done at 50 DEG C
Dry 24-48h finished products.
Wherein step 1)The natural flake graphite is 60-200 mesh;
The consumption of the concentrated sulfuric acid is pressed per the 1kg natural flake graphites 10L concentrated sulfuric acids;
The consumption of the potassium peroxydisulfate is the 45% of natural flake graphite weight;
The consumption of the phosphorus pentoxide is the 50% of natural flake graphite weight;
The consumption of the water is 4 times of concentrated sulfuric acid volume;
The mass fraction of the hydrogen peroxide is 30%, and consumption is 0.18 times of concentrated sulfuric acid volume.
Step 2)The consumption of the thionyl chloride is pressed per 1kg graphene oxides 8L thionyl chlorides.
Step 3)The consumption of the 1,3- propane diamine is the 65% of surface graphene containing acid chloride groups weight;
The consumption of the N, N '-dimethylformamide press per graphene of the 1kg surfaces containing acid chloride groups with 4.3 L N, N '-
Dimethylformamide.
Step 4)The consumption of the Cyanuric Chloride is 60% of surface with amino graphene weight;
The consumption of the tetrahydrofuran is pressed per the 1kg surfaces 3.9L tetrahydrofurans of the graphene with amino.
Step 5)The consumption of the N, N '-dimethylformamide is pressed per 1kg surfaces 2.2 L of the graphene containing triazine ring
N, N '-dimethylformamide;
In the N containing diatomic alcohol compounds, N '-dimethyl formamide solution, the consumption of the diatomic alcohol compounds is table
The 70% of the face weight of graphene containing triazine ring, N used, the amount of N '-dimethylformamide is pressed to be used per 1kg diatomic alcohol compounds
1.3L N, N '-dimethylformamide.
The diatomic alcohol compounds are any one in ethylene glycol, 1,3- propane diols, l, 4- butanediols.
The preferred KH-570 silane couplers of silane coupler(That is γ-(Methacryloxypropyl)Propyl trimethoxy silicon
Alkane), consumption is excessive, cost can be caused too high, and the competitiveness of product declines;Consumption is too small, can influence forming silane film speed and matter
Amount, therefore the preferred 0.8-1.0 % of its consumption.
Adhesion promoter is from double (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters.
Complex compound selects disodium ethylene diamine tetraacetate.
Fluoride is sodium fluoride and hydrofluoric acid by weight 1:(0.8-1.2)Mix, water is that electrical conductivity is less than 5 μ s/
Cm deionized water.
The preparation method of graphene silane filming agent of the present invention in turn includes the following steps:
(1)1/5-1/4 all with water is first added in a kettle., is added modified graphene, is stirred 2-3 hours;
(2)Gui alkane Ou Lian Ji ﹑ adhesion promoters are added, are stirred 7-8 hours;
(3)Fluoride is added, is stirred 0.5-1 hours;
(4)Complex compound is added, is stirred 2-3 hours;
(5)Remaining water is finally supplied to stir.
Application method:Graphene silane filming agent of the present invention is converted into deionized water(Electrical conductivity is less than 5 μ s/cm), graphene
The weight ratio of silane filming agent and water is 1:10-1:20, taken out after pending workpiece is soaked wherein 3 minutes, workpiece surface is obtained
Obtain graphene-organosilan hybridized film of one layer of uniform and delicate.
Beneficial effects of the present invention are as follows:
Graphene-organosilan hybridized film of the graphene silane filming agent formation of the present invention is than traditional crystal type phosphating coat and nothing
Phosphorus conversion film properties will be much better.Have good attached between graphene-organosilan hybridized film and Jin category Biao Mian ﹑ painting layers
Put forth effort, it is better with without phosphorus conversion film than conventional phosphatizing film.Graphene-organosilan hybridized film decay resistance is also than traditional phosphorus
Change film and without phosphorus conversion film is strong more than ten times, be specifically shown in Table 1.
Table 1
Embodiment
Below by embodiment, the invention will be further described, but not as a limitation of the invention.
1-11 of embodiment of the present invention formula is shown in Table 2, table 3 respectively, and wherein adhesion promoter is double (dioctylphyrophosphoric acids
Acyloxy) ethylene titanate esters, the trade mark is HY311, and water is deionized water.
Wherein the hydroxy radical content of modified graphene is 0.009%, and preparation method is as follows:
1)The natural flake graphite of the mesh of 1000 g 100 is added in the 10 L concentrated sulfuric acids at 2 DEG C and stirs 2 h;Then it is slow
Add and 3 h are stirred at 450 g potassium peroxydisulfates and 500 g phosphorus pentoxides, 23 DEG C, then be warming up at 43 DEG C and stir 24 h, so
After be slowly added to 40 L water and stir 2 h, be slow added into 1.8 L mass fractions for 30% hydrogen peroxide, obtain bright orange coloured particles
The suspension of thing;The centrifugation of glassy yellow particulate matter is separated, after being eluted with water, 16h is dried in vacuo at 62 DEG C, obtains graphene oxide
990g;
2)Graphene oxide 985g is added in 7.88 L thionyl chlorides, the h of return stirring 28 at 80 DEG C, be then centrifuged for point
From, through acetone clean after, 14 h are dried in vacuo at room temperature, graphene 980g of the surface containing acid chloride groups is obtained;
3)Graphene 980g and 637g 1,3- propane diamine of the surface containing acid chloride groups is added separately to 4.2 L N, N '-two
In NMF, under nitrogen protection, 30h is stirred at 80 DEG C, then remove N, N '-dimethyl formamide, through washing under reduced pressure
After net, 30h is dried in vacuo at room temperature, graphene 963g of the surface with amino is obtained;
4)Graphene 960g and 576g Cyanuric Chloride of the surface with amino is added separately to 3.74L tetrahydrofurans at 1 DEG C
In, after stirring reaction 30h, remove tetrahydrofuran under reduced pressure, after being cleaned through ether, 15h is dried in vacuo at 12 DEG C, obtain surface containing three
The graphene 926g of piperazine ring;
5)By graphene 920g of the surface containing triazine ring in 2 L N, N '-dimethylformamide after stirring and dissolving, at 40 DEG C
Under in the N for 0.84L is slowly dropped in 6h containing 644g ethylene glycol, N '-dimethyl formamide solution, after completion of dropping
In 45 DEG C of isothermal reaction 24h, then 90 DEG C of isothermal reaction 36h are warming up to, remove solvent under reduced pressure, after being cleaned through distilled water, at 50 DEG C
30h is dried in vacuo, the hydroxyl water-soluble modified graphene in surface is made;In the modified graphene, the content of hydroxyl is
0.009%。
The embodiment 1-6 of table 2 formula, %
。
The embodiment 7-11 of table 3 formula
。
Comparative example 1
Comparative example 1 increases the consumption of hydrofluoric acid on the basis of embodiment 11, eliminates sodium fluoride.
Comparative example 2
Disodium ethylene diamine tetraacetate is replaced with citric acid, consumption and ethylenediamine tetrem by comparative example 2 on the basis of embodiment 11
Acid disodium is identical.
Comparative example 3
Silane coupling reagent KH-570 is replaced with KH-560 γ-glycidyl ether oxygen third by comparative example 3 on the basis of embodiment 11
Base trimethoxy silane, consumption is identical with KH-570.
Comparative example 4
Modified graphene is changed to modified graphene preparation process 1 by comparative example 4 on the basis of embodiment 11)In obtained oxidation
Graphene is other constant.
The preparation method of the embodiment of the present invention and comparative example is as follows:
(1)First add in a kettle. all with the 1/5 of water, add modified graphene, stir 2 hours;
(2)Gui alkane Ou Lian Ji ﹑ adhesion promoters are added, are stirred 8 hours;
(3)Fluoride is added, is stirred 0.5 hour;
(4)Complex compound is added, is stirred 2 hours;
(5)Remaining water is finally supplied to stir.
1-11 of embodiment of the present invention using effect is shown in Table 4, table 5, and the effect of comparative example is shown in Table 6, with by graphite when using
Alkene silane filming agent converts deionized water, and the weight ratio of graphene silane filming agent and water is 1:20, by pending workpiece(It is cold rolling thin
Plate)Immersion is taken out after wherein 3 minutes.
The embodiment 1-6 of table 4 using effect
。
The embodiment 7-11 of table 5 using effect
。
The comparative example 1-4 of table 6 using effect
。
Consolidated statement 4-6 can be seen that graphene of the present invention-organosilan hybridized film decay resistance than conventional phosphatizing film and
Without phosphorus conversion film is strong more than ten times.
Comparative run purpose method of testing is as follows in table:
Phosphorization membrane thickness and microstructure are analyzed using LEO SEM;
Using METTLER TOLEDO electronic balances(Precision is 0.0001)Phosphorization film weight is analyzed;
Test piece impact and bending property are analyzed using paint film impact and toughness analyzer;
Cupric sulphate dropping test method is GB5936-86;
3% sodium chloride erosion test is performed by GB6817-96;
Salt spray test method of testing is GB/T10125-97;
Evaluated with line plate wet-heat resisting adhesive force (i.e. secondary adhesive force test) by GB/T 9286.
Claims (10)
1. a kind of graphene silane filming agent, it is characterised in that by percentage to the quality, is made up of following raw material:Modified graphene
0.08-0.18%;Silane coupler 0.6-1.1%;Adhesion promoter 0.3-0.8%;Complex compound 1.6-2.2%;Fluoride 0.8-
1.0%;Surplus is water.
2. graphene silane filming agent according to claim 1, it is characterised in that the modified graphene carries for surface
The water-soluble graphene of hydroxyl, wherein hydroxy radical content are 0.005-0.012%.
3. graphene silane filming agent according to claim 1, it is characterised in that the consumption of the modified graphene is
0.10-0.15%。
4. graphene silane filming agent according to claim 1, it is characterised in that the silane coupler is KH-570 silicon
Alkane coupling agent.
5. graphene silane filming agent according to claim 1, it is characterised in that the silane coupler consumption is 0.8-
1.0%。
6. graphene silane filming agent according to claim 1, it is characterised in that adhesion promoter is double (dioctyl Jiao
Phosphoric acid acyloxy) ethylene titanate esters.
7. graphene silane filming agent according to claim 1, the complex compound is disodium ethylene diamine tetraacetate.
8. graphene silane filming agent according to claim 1, it is characterised in that fluoride is that sodium fluoride is pressed with hydrofluoric acid
Weight compares 1:(0.8-1.2)Mix.
9. graphene silane filming agent according to claim 1, it is characterised in that diluted when using with deionized water, graphite
The weight ratio of alkene silane filming agent and deionized water is 1:10-1:20.
10. the preparation method of graphene silane filming agent according to claim 1, it is characterised in that successively including following step
Suddenly:
(1)1/5-1/4 all with water is first added in a kettle., is added modified graphene, is stirred 2-3 hours;
(2)Gui alkane Ou Lian Ji ﹑ adhesion promoters are added, are stirred 7-8 hours;
(3)Fluoride is added, is stirred 0.5-1 hours;
(4)Complex compound is added, is stirred 2-3 hours;
(5)Remaining water is finally supplied to stir.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710390309.XA CN107217249A (en) | 2017-05-27 | 2017-05-27 | Graphene silane filming agent and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710390309.XA CN107217249A (en) | 2017-05-27 | 2017-05-27 | Graphene silane filming agent and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107217249A true CN107217249A (en) | 2017-09-29 |
Family
ID=59946866
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710390309.XA Pending CN107217249A (en) | 2017-05-27 | 2017-05-27 | Graphene silane filming agent and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107217249A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107841739A (en) * | 2017-11-20 | 2018-03-27 | 湖南金裕环保科技有限公司 | Fluorinated graphene surface conditioning agent, preparation method and its application method |
CN108411294A (en) * | 2018-03-22 | 2018-08-17 | 上海利物盛纳米科技有限公司 | Pretreatment fluid and its preparation and application before a kind of environment-friendly type metal application |
CN108796571A (en) * | 2018-06-20 | 2018-11-13 | 上海理工大学 | A method of corrosion stability of magnesium alloy is improved using nitrogen-doped graphene quantum dot coating |
CN114574847A (en) * | 2022-04-07 | 2022-06-03 | 东莞市精诚环保科技有限公司 | Novel graphene film-forming agent and preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104058398A (en) * | 2014-07-15 | 2014-09-24 | 福建江夏学院 | Modified graphene and preparation method thereof |
CN106011816A (en) * | 2016-06-29 | 2016-10-12 | 苏州禾川化学技术服务有限公司 | Graphene-based coating agent |
CN106399991A (en) * | 2016-08-30 | 2017-02-15 | 广州市卡帕尔表面处理科技有限公司 | Silane nano-graphene ceramic film and preparation method thereof |
-
2017
- 2017-05-27 CN CN201710390309.XA patent/CN107217249A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104058398A (en) * | 2014-07-15 | 2014-09-24 | 福建江夏学院 | Modified graphene and preparation method thereof |
CN106011816A (en) * | 2016-06-29 | 2016-10-12 | 苏州禾川化学技术服务有限公司 | Graphene-based coating agent |
CN106399991A (en) * | 2016-08-30 | 2017-02-15 | 广州市卡帕尔表面处理科技有限公司 | Silane nano-graphene ceramic film and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
国家知识产权局专利复审委员会: "《专利复审和无效审查决定汇编(2009)·光电(第一卷)》", 31 May 2016, 知识产权出版社 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107841739A (en) * | 2017-11-20 | 2018-03-27 | 湖南金裕环保科技有限公司 | Fluorinated graphene surface conditioning agent, preparation method and its application method |
CN108411294A (en) * | 2018-03-22 | 2018-08-17 | 上海利物盛纳米科技有限公司 | Pretreatment fluid and its preparation and application before a kind of environment-friendly type metal application |
CN108796571A (en) * | 2018-06-20 | 2018-11-13 | 上海理工大学 | A method of corrosion stability of magnesium alloy is improved using nitrogen-doped graphene quantum dot coating |
CN114574847A (en) * | 2022-04-07 | 2022-06-03 | 东莞市精诚环保科技有限公司 | Novel graphene film-forming agent and preparation method and application thereof |
CN114574847B (en) * | 2022-04-07 | 2023-10-24 | 东莞市精诚环保科技有限公司 | Novel graphene film forming agent and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107217249A (en) | Graphene silane filming agent and preparation method thereof | |
CN106011816B (en) | A kind of graphene-based film agent | |
CN103205738B (en) | A kind of chromium-free passivation liquid | |
CN102070927B (en) | Water-based surface treatment agent for color coating pretreatment of galvanized plates | |
CN102876167B (en) | Aqueous silvery aluminum powder flashing paint | |
CN104561970A (en) | Corrosion-resistant magnesium aluminum alloy chromium-free passivation solution | |
CN106906462B (en) | A kind of metal surface pretreating reagent and preparation method thereof, application | |
CN101481553A (en) | Normal temperature cured self-assembly composite nano oxide anti-corrosive paint | |
CN103031056B (en) | A kind of Metal surface silane treatment agent containing water nano zinc oxide material and preparation method thereof | |
CN102586769B (en) | A kind of phosphate-free metal surface treatment agent and using method thereof | |
CN109778167B (en) | Trivalent chromium passivator with excellent coating performance and preparation method thereof | |
CN109321908A (en) | A kind of metal surface multifunction environment-protection type nanometer vitrification liquid and preparation method thereof and application method | |
CN103938198A (en) | Phosphorus-free nano vitrification agent, and preparation method and application thereof | |
CN110157269B (en) | Steel structure anticorrosion construction process | |
CN107012453B (en) | A kind of method that green low temperature quickly prepares phosphating coat | |
CN105734547A (en) | Environment-friendly metal surface treating agent and preparation method thereof | |
CN109097761B (en) | Environment-friendly nano coating agent and preparation method thereof | |
CN107119268A (en) | Graphene phosphate agent and preparation method thereof | |
CN107475704B (en) | Metal surface silane treatment agent and preparation method thereof | |
CN103073969A (en) | Epoxy resin antirust paint and preparation method thereof | |
CN106835093B (en) | A kind of Q type POSS modified metal surface pretreating reagent and preparation method thereof, application | |
CN104278260B (en) | A kind of silanization treating agent for aluminum alloy surface and preparation method thereof | |
CN107142472A (en) | Graphene nano film agent and preparation method thereof | |
CN106894009B (en) | A kind of epoxy group POSS modified metal surface pretreating reagent and preparation method thereof, application | |
CN103031551B (en) | A kind of metal surface silane finish that contains ethylenediamine tetramethylene fork Alendronate and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170929 |
|
RJ01 | Rejection of invention patent application after publication |