CN107841739A - Fluorinated graphene surface conditioning agent, preparation method and its application method - Google Patents
Fluorinated graphene surface conditioning agent, preparation method and its application method Download PDFInfo
- Publication number
- CN107841739A CN107841739A CN201711155721.XA CN201711155721A CN107841739A CN 107841739 A CN107841739 A CN 107841739A CN 201711155721 A CN201711155721 A CN 201711155721A CN 107841739 A CN107841739 A CN 107841739A
- Authority
- CN
- China
- Prior art keywords
- fluorinated graphene
- conditioning agent
- surface conditioning
- graphene surface
- 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 fluorinated graphene surface conditioning agent, by percentage to the quality, it is made up of following raw material：Fluorinated graphene 0.03 0.09%, fluosilicic acid 1.2 2.2%, ocratation 0.3 0.8%, aluminate coupling agent 0.16 0.23%, sodium fluoride 0.8 1.0%, surplus is deionized water.There is good adhesion between fluorinated graphene amorphous membrance and Jin category Biao Mian ﹑ painting layers that the fluorinated graphene surface conditioning agent is formed, than conventional phosphatizing film and without phosphorus several ten times of conversion film；Fluorinated graphene amorphous membrance decay resistance is also than more than ten times of conventional phosphatizing film and without phosphorus conversion film.
Description
Technical field
The present invention relates to metal conditioner field, in particular, is related to a kind of in metal surface formation nanoscale
The fluorinated graphene surface conditioning agent of other chemical composition coating.
Background technology
Metal surface pre-treatment at present is most of using phosphating process, with the continuous propulsion of energy-saving and emission-reduction, tradition
Phosphating process is withdrawn from the market constantly；The surface treatment of the phosphate-free metals such as emerging zirconium system, zirconium titanium system, silane system, silane zirconium system
Agent, market has been captured rapidly；But the properties of these without phosphorus conversion films are suitable with conventional phosphatizing film properties, without superiority,
Can not meet the needs of high anti-corrosion industry application such as ship.
The content of the invention
An object of the present invention is overcome the deficiencies in the prior art, there is provided a kind of fluorinated graphene surface conditioning agent,
Have between fluorinated graphene amorphous membrance and Jin category Biao Mian ﹑ painting layers that the fluorinated graphene surface conditioning agent is formed good
Adhesion, than conventional phosphatizing film and without phosphorus several ten times of conversion film；Fluorinated graphene amorphous membrance decay resistance also than
More than ten times of conventional phosphatizing film and without phosphorus conversion film.
The second object of the present invention is the preparation method for providing above-mentioned fluorinated graphene surface conditioning agent.
The third object of the present invention is the application method for providing above-mentioned fluorinated graphene surface conditioning agent.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of fluorinated graphene surface conditioning agent, by percentage to the quality, it is made up of following raw material：
Fluorinated graphene 0.03-0.09%,
Fluosilicic acid 1.2-2.2%,
Ocratation 0.3-0.8%,
Aluminate coupling agent 0.16-0.23%,
Sodium fluoride 0.8-1.0%,
Deionized water surplus.
The preferred 0.05-0.08% of dosage of the fluorinated graphene, fluorinated graphene dosage is too low, and film layer porosity is big, dredges
Pine；Modified graphene dosage is too high, film layer and metallic matrix poor adhesive force.
The preparation method of the fluorinated graphene is as follows：With specific surface area 250-350cm2/ g honeycomb-shaped oxidizing graphene
And F2For raw material, whole course of reaction is carried out in stainless steel closed chamber, reacts the oxygen in initial logical nitrogen exclusion reative cell
And moisture, then lead to N at room temperature2/F2Mixed gas, be volume ratio 1:（1-3）, finally with 4-5 DEG C/min programming rate
Being heated to 180 DEG C makes it be fluorinated 4-6 hours, and final F, C atomic ratio are 1.0, there is the fluorination that 8-12% is individual layer in products therefrom
Graphene, remaining number of plies are 2-5 layers.
Water is the deionized water that electrical conductivity is less than 5 μ s/cm.
The preparation method of fluorinated graphene surface conditioning agent of the present invention, in turn includes the following steps：
（1）First add in a kettle all with the 1/5-1/4 of water, add fluorinated graphene, stir 2-3 hours；
（2）Aluminate Ou Lian Ji ﹑ fluosilicic acid, ocratation are added, stirs 7-8 hours；
（3）Sodium fluoride is added, stirs 0.5-1 hours；
（4）Remaining water is finally supplied to stir.
Application method：Fluorinated graphene surface conditioning agent of the present invention is converted into deionized water（Electrical conductivity is less than 5 μ s/cm）, fluorine
The weight of graphite alkene surface conditioning agent and water ratio is 1:10-1:20, taken out after pending workpiece is soaked wherein 3 minutes, work
Part surface obtains the fluorinated graphene amorphous membrance of one layer of uniform and delicate.
Beneficial effects of the present invention are as follows：The fluorinated graphene that the fluorinated graphene surface conditioning agent of the present invention is formed is without fixed
Shape film will be excellent than traditional crystal type phosphating coat and without phosphorus conversion film properties；Fluorinated graphene amorphous membrance and Jin category Biao Mian ﹑
There is good adhesion between painting layer, than conventional phosphatizing film and without phosphorus several ten times of conversion film；Fluorinated graphene is without fixed
Shape film decay resistance is also than more than ten times of conventional phosphatizing film and without phosphorus conversion film；Specifically it is shown in Table 1.
Table 1
。
Embodiment
Below by embodiment, the invention will be further described, but not as a limitation of the invention.
The preparation method of fluorinated graphene is as follows in embodiment：
With specific surface area 300cm2/ g honeycomb-shaped oxidizing graphene and F2For raw material, whole course of reaction is in stainless steel closed chamber
Interior progress, oxygen and moisture in initial logical nitrogen exclusion reative cell are reacted, then leads to N at room temperature2/F2Mixed gas, be
Volume ratio 1:2, being finally heated to 180 DEG C with 4 DEG C/min programming rate makes it be fluorinated 5 hours, and final F, C atomic ratio are
1.0, there is 10% fluorinated graphene for being individual layer in products therefrom, remaining number of plies is 2-5 layers.
1-9 of embodiment of the present invention formula is shown in Table 2, table 3 respectively, and water is deionized water.
The embodiment 1-6 of table 2 formula, %
。
The embodiment 7-9 of table 3, comparative example 1-3 formula, %
。
Comparative example 1
Comparative example 1 replaces with fluorinated graphene on the basis of embodiment 9 graphene oxide of production fluorinated graphene, its
It is same as Example 9.
Comparative example 2
Comparative example 2 increases the dosage of fluorinated graphene on the basis of embodiment 9, other same as Example 9.
Comparative example 3
Fluosilicic acid is replaced with hydrofluoric acid by comparative example 3 on the basis of embodiment 9, and dosage is identical with fluosilicic acid.
The preparation method of fluorinated graphene surface conditioning agent of the present invention in turn includes the following steps：
（1）In a kettle first add all use the 1/4 of water, addition fluorinated graphene, stirring 3 hours；
（2）Aluminate coupling agent F-1 ﹑ fluosilicic acid, ocratation are added, is stirred 8 hours；
（3）Sodium fluoride is added, is stirred 1 hour；
（4）Remaining water is finally supplied to stir.
The embodiment of the present invention, the using effect of comparative example are shown in Table 4, table 5, with by fluorinated graphene surface conditioning agent during use
Convert deionized water, the weight ratio of fluorinated graphene surface conditioning agent and water is 1:20, by pending workpiece（Flat cold-rolled sheet）Immersion
Taken out after wherein 3 minutes.
The embodiment 1-6 of table 4 using effect
。
The embodiment 7-9 of table 5, comparative example 1-3 using effect
。
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.
Above content describes the general principle and principal character of the present invention, and the present invention is not limited to the above embodiments,
Without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, and these changes and improvements are all
Fall into scope of the claimed invention.The claimed scope of the invention is by appended claims and its equivalent circle
It is fixed.
Claims (9)
1. a kind of fluorinated graphene surface conditioning agent, by percentage to the quality, it is made up of following raw material：Fluorinated graphene 0.03-
0.09%, fluosilicic acid 1.2-2.2%, ocratation 0.3-0.8%, aluminate coupling agent 0.16-0.23%, sodium fluoride 0.8-1.0%,
Surplus is water.
2. fluorinated graphene surface conditioning agent according to claim 1, it is characterised in that the dosage of the fluorinated graphene
For 0.05-0.08%.
3. fluorinated graphene surface conditioning agent according to claim 1, it is characterised in that the preparation of the fluorinated graphene
Method is as follows：With specific surface area 250-350cm2/ g honeycomb-shaped oxidizing graphene and F2For raw material, whole course of reaction is stainless
Carried out in steel closed chamber, the initial logical nitrogen of reaction excludes oxygen and moisture in reative cell, then leads to N at room temperature2/F2It is mixed
Gas is closed, is volume ratio 1:（1-3）, being finally heated to 180 DEG C with 4-5 DEG C/min programming rate makes it be fluorinated 4-6 hours, most
Whole F, C atomic ratio are 1.0, have the fluorinated graphene that 8-12% is individual layer in products therefrom, remaining number of plies is 2-5 layers.
4. fluorinated graphene surface conditioning agent according to claim 1, it is characterised in that by percentage to the quality, by following
Raw material is made：Fluorinated graphene 0.075%, fluosilicic acid 1.65%, ocratation 0.65%, aluminate coupling agent 0.185%, sodium fluoride
0.9%, surplus is deionized water.
5. fluorinated graphene surface conditioning agent according to claim 1, it is characterised in that water is that electrical conductivity is less than 5 μ s/cm
Deionized water.
6. the preparation method of fluorinated graphene surface conditioning agent according to claim 1, it is characterised in that include successively such as
Lower step：
（1）First add in a kettle all with the 1/5-1/4 of water, add fluorinated graphene, stir 2-3 hours；
（2）Aluminate Ou Lian Ji ﹑ fluosilicic acid, ocratation are added, stirs 7-8 hours；
（3）Sodium fluoride is added, stirs 0.5-1 hours；
（4）Remaining water is finally supplied to stir.
7. the preparation method of fluorinated graphene surface conditioning agent according to claim 6, it is characterised in that include successively such as
Lower step：
（1）In a kettle first add all use the 1/4 of water, addition fluorinated graphene, stirring 3 hours；
（2）Aluminate Ou Lian Ji ﹑ fluosilicic acid, ocratation are added, is stirred 8 hours；
（3）Sodium fluoride is added, is stirred 1 hour；
（4）Remaining water is finally supplied to stir.
8. the application method of fluorinated graphene surface conditioning agent according to claim 1, it is characterised in that comprise the following steps：
Fluorinated graphene surface conditioning agent is converted into deionized water, the weight ratio of fluorinated graphene surface conditioning agent and water is 1:10-1:20,
It will be taken out after pending workpiece immersion wherein 3-5 minutes.
9. the application method of fluorinated graphene surface conditioning agent according to claim 1, it is characterised in that comprise the following steps：
Fluorinated graphene surface conditioning agent is converted into deionized water, the weight ratio of fluorinated graphene surface conditioning agent and water is 1:20, it will treat
Processing workpiece flat cold-rolled sheet takes out after soaking wherein 3 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711155721.XA CN107841739A (en) | 2017-11-20 | 2017-11-20 | Fluorinated graphene surface conditioning agent, preparation method and its application method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711155721.XA CN107841739A (en) | 2017-11-20 | 2017-11-20 | Fluorinated graphene surface conditioning agent, preparation method and its application method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107841739A true CN107841739A (en) | 2018-03-27 |
Family
ID=61679803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711155721.XA Pending CN107841739A (en) | 2017-11-20 | 2017-11-20 | Fluorinated graphene surface conditioning agent, preparation method and its application method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107841739A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104962899A (en) * | 2015-07-17 | 2015-10-07 | 青岛格瑞烯金属防护科技有限公司 | Phosphorus-free graphene-oxide-containing metal surface pretreatment solution and application method thereof |
| CN105839092A (en) * | 2016-05-31 | 2016-08-10 | 无锡伊佩克科技有限公司 | Steel surface zirconium oxide conversion plating solution and preparing method thereof |
| CN106086820A (en) * | 2016-07-26 | 2016-11-09 | 厦门烯成石墨烯科技有限公司 | A kind of preparation method of the fluorinated graphene composite being loaded with nanometer silver |
| CN107217249A (en) * | 2017-05-27 | 2017-09-29 | 湖南金裕环保科技有限公司 | Graphene silane filming agent and preparation method thereof |
-
2017
- 2017-11-20 CN CN201711155721.XA patent/CN107841739A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104962899A (en) * | 2015-07-17 | 2015-10-07 | 青岛格瑞烯金属防护科技有限公司 | Phosphorus-free graphene-oxide-containing metal surface pretreatment solution and application method thereof |
| CN105839092A (en) * | 2016-05-31 | 2016-08-10 | 无锡伊佩克科技有限公司 | Steel surface zirconium oxide conversion plating solution and preparing method thereof |
| CN106086820A (en) * | 2016-07-26 | 2016-11-09 | 厦门烯成石墨烯科技有限公司 | A kind of preparation method of the fluorinated graphene composite being loaded with nanometer silver |
| CN107217249A (en) * | 2017-05-27 | 2017-09-29 | 湖南金裕环保科技有限公司 | Graphene silane filming agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3175964A (en) | Surface treatment of metal article by water-soluble (film-forming) material | |
| Zheludkevich et al. | Corrosion protective properties of nanostructured sol–gel hybrid coatings to AA2024-T3 | |
| CN110359044B (en) | Preparation method of steel matrix surface super-hydrophobic film | |
| WO2017000315A1 (en) | Titanium-zirconium coloured chromium-free passivation solution for surface treatment of aluminium alloy, method for treating aluminium alloy surface using same, and use thereof | |
| Pak et al. | Fabrication of environmentally friendly anti-corrosive composite coatings on AZ31B Mg alloy by plasma electrolytic oxidation and phytic acid/3-aminopropyltrimethoxysilane post treatment | |
| JP5620476B2 (en) | Methods and compositions for treating metal surfaces | |
| CN103205738A (en) | Non-chrome purified liquid | |
| CN106906462B (en) | A kind of metal surface pretreating reagent and preparation method thereof, application | |
| CN104532226A (en) | Environment-friendly organic-inorganic hybrid aluminum alloy primer and preparation method thereof | |
| CN111593335A (en) | Improved zirconium-based conversion film for metal surface treatment and preparation method and application thereof | |
| CN106835093B (en) | A kind of Q type POSS modified metal surface pretreating reagent and preparation method thereof, application | |
| MX2010011889A (en) | Process for production of tin-plated steel sheets, tin-plated steel sheets and chemical conversion treatment fluid. | |
| CN111197176B (en) | Electrochemical treatment method of copper foil and composite copper foil material | |
| CN106894009B (en) | A kind of epoxy group POSS modified metal surface pretreating reagent and preparation method thereof, application | |
| CN105925969A (en) | Treating fluid for rapidly preparing non-ferrous composite conversion film on surface of aluminum alloy and treating method | |
| CN113201731A (en) | Method for quickly forming zirconium film on surface of high-strength steel for automobile | |
| CN107841739A (en) | Fluorinated graphene surface conditioning agent, preparation method and its application method | |
| JP3737168B2 (en) | Manufacturing method of electrogalvanized steel sheet with high whiteness and excellent paintability | |
| Hao et al. | Preparation of metal organic framework film on surface of aluminum profile and properties of fluorocarbon powder coating | |
| CN105803440B (en) | A kind of carbon steel, galvanized sheet, aluminium are the same as rooved face pretreating agent, preparation method and metal surface pretreatment | |
| CN114892152A (en) | Method for preparing ionic liquid conversion film on surface of magnesium alloy | |
| Liu et al. | Design of a smart protective coating with molybdate-loaded halloysite nanotubes towards corrosion protection in reinforced concrete | |
| CN107326354A (en) | A kind of silane finish and preparation method thereof | |
| Fang et al. | Study on the effect of acetate ions on the sealing treatment for anodic oxide film of 6063 aluminum alloy | |
| CN112626588A (en) | Wear-resistant and corrosion-resistant cathode electrophoresis coating process |
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: 20180327 |
|
| RJ01 | Rejection of invention patent application after publication |