CN109836919A - A kind of functional graphene oxide corrosion-inhibiting coating and its preparation process - Google Patents
A kind of functional graphene oxide corrosion-inhibiting coating and its preparation process Download PDFInfo
- Publication number
- CN109836919A CN109836919A CN201710932359.6A CN201710932359A CN109836919A CN 109836919 A CN109836919 A CN 109836919A CN 201710932359 A CN201710932359 A CN 201710932359A CN 109836919 A CN109836919 A CN 109836919A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- coating
- method described
- corrosion
- functional
- 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.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of functional graphene oxide corrosion-inhibiting coating and its preparation processes, it is characterized by: preparing anticorrosive paint using modified graphene oxide, inorganic nano-particle, film forming matter etc., coating is equably brushed by the method for brushing by the corrosion-inhibiting coating excellent to forming properties on non-corrosive metal (NCM) surface.Key step is as follows: (1) graphene oxide of preparation being carried out functional modification；(2) functional graphene oxide is dissolved in organic solvent, ultrasonic disperse obtains uniform graphene oxide dispersion；(3) inorganic nano-particle ultrasonic disperse is added；(4) film forming matter stirring is added and instills a certain amount of surface modifier and curing agent after a certain period of time to reduce the surface of coating energy, proper quantity of defoaming agent removes the bubble in solution；(5) stop stirring, stand, using on the method for brushing metal plate of equably brushing that treated, room temperature curing can form the coating with excellent antiseptic property.The preparation process is simple and convenient to operate, and preservative efficiency is high.
Description
Technical field
It is synthetically prepared technical field the invention belongs to graphene anticorrosive paint, it is anti-to be related to a kind of functional graphene oxide
Rotten coating and its preparation process.
Background technique
Graphene has excellent electric conductivity, mechanical property, thermal stability and screen effect, may act as functionality and fills out
Material, to enhance the performance of coating.Graphene has following advantage as corrosion-resistant functional filler: (1) small-size effect is received
Meter level small size can make it be filled into the hole in coating, defect；(2) large specific surface area, graphene belong to lamellar structure, tool
There is biggish specific surface area, barrier big one by one can be formed, effect is higher than mica flake；(3) barrier property is excellent, graphene
It is to be made of multiple carbon atom hexatomic rings, there is stable conjugated structure, not hydrophilic also not oleophylic can resists extraneous erosion
Matter penetrates into metal surface, and still, when defective coatings, the electric conductivity of graphene promotes metal erosion instead.Graphene
As corrosion-resistant functional filler, there are also disadvantages: (1) poor dispersion of graphene, easily forms defect in the coating；(2)
There may be electronics transfers between graphene, metal；(3) compatibility of graphene and other polymers is poor；These disadvantages
It is limited in the application in many fields.So carrying out functional modification to it for the screen effect for preferably utilizing graphene
It is necessary.Compared to graphene, the more some oxygen-containing functional groups of graphene oxide, and oxygen-containing functional group can just be made
For the active site of reaction, functional modification is carried out to graphene oxide using small-molecule substance, oxidation on the one hand can be improved
The dispersibility of graphene is distributed it uniformly in the coating；On the other hand p-phenylenediamine etc. is grafted by oxygen-containing group
Its electric conductivity can be reduced, the generation of corrosion is prevented.In addition, the addition of inorganic nano-particle can also be improved the hydrophobic of coating
Property, resistance tocrocking, and then improve antiseptic property.
Summary of the invention
The purpose of the present invention is to provide a kind of functional graphene oxide corrosion-inhibiting coating of favorable dispersibility and its preparations
Method.
Technical scheme is as follows: graphene oxide is prepared using improved Hummers method first, then with to benzene
Diamines carries out graft modification to it by the method that hydro-thermal flows back, and obtained product is dissolved in methanol solution, while being added poly-
Vinyl butyral, silica and titanium oxide inorganic nanoparticle, dimethyl silicone polymer are configured to solution, and stirring is certain
Time is equably coated on metal plate, room temperature curing one day, so that it may it is excellent to obtain anti-corrosion after standing de-bubble using the method for brushing
Good coating.
Main innovation point of the invention is as follows: improving it to graphene oxide graft modification with small-molecule substance and is polymerizeing
Dispersibility in object, then combine with inorganic nano-particle silica, titanium dioxide etc., act synergistically anti-corrosion, while with poly- two
The interactions such as methylsiloxane prepolymer reduce the surface energy of coating, the common antiseptic property for improving coating.
The method that functional graphene oxide is prepared in the method for the present invention is as follows: using graphite powder as raw material, use is improved
Hummers method prepares graphene oxide, prepares certain density graphene oxide water solution, using ultrasonic disperse certain time,
P-phenylenediamine is added later, under alkaline condition, when certain temperature, is stirred at reflux certain time, finally filter, clean, freezing it is dry
It is dry to obtain the graphene oxide of functionalization.
The preparation process of functional graphene oxide anticorrosive paint is as follows in the method for the present invention: by the oxygen of obtained functionalization
Graphite alkene is dissolved in methanol solution, water bath sonicator certain time；Add polyvinyl butyral, silica, titanium dioxide
Titanium, dimethyl silicone polymer continuously stir and longer obtain anticorrosive paint.
The preparation process of functional graphene oxide corrosion-inhibiting coating is as follows in the method for the present invention: will be upper using the method brushed
It states anticorrosive paint to brush onto treated metal plate, solidify 24 hours at room temperature, so that it may obtain anti-corrosion in metal surface
The coating haveing excellent performance.
Reagent used in the present invention and material: graphite powder, potassium permanganate, sodium nitrate, the concentrated sulfuric acid, dilute hydrochloric acid, hydrogen peroxide, right
Phenylenediamine, ammonium hydroxide are to analyze pure, inorganic nano-particle silica, titanium dioxide, polyvinyl butyral, poly dimethyl
Siloxane prepolymer, oil paint defoaming agent B-457.
Detailed description of the invention
Fig. 1 is the anticorrosion mechanism figure of prepares coating.
Fig. 2 is the nyquist diagram of the modified graphene oxide corrosion-inhibiting coating of different content.
Fig. 3 is the corrosion rate figure of the modified graphene oxide corrosion-inhibiting coating of different content.
Specific embodiment
It elaborates below with reference to specific example to the present invention.
Example 1: using Hummers method is improved, using graphite powder as raw material, graphene oxide dispersion is prepared.Functionalization oxygen
The preparation of graphite alkene, prepares the graphene oxide solution that 100 milliliters of concentration are 0.4% first, 500W ultrasound 30 minutes, then plus
Enter 3.0 grams of p-phenylenediamine, under alkaline condition, stirring, reflux 3 hours at 95 DEG C of temperature filter, cleaned respectively with water and ethyl alcohol
Three to five times, freeze-drying 24 hours to get arrive modified graphene oxide；The modified graphene oxide of 16mg is put into 20ml first
In alcoholic solution, water bath sonicator disperses 1 hour, and 2.0g silica, 0.5g titanium dioxide, 2.0g polyvinyl alcohol contracting fourth are added later
Aldehyde, 0.16g polydimethylsiloxane prepolymer object magnetic agitation 20 hours, defoaming agent B-457 are added later and is stirred for 30min, quiet
1 hour removing bubble is set, obtaining modified graphene oxide content is 0.8% anticorrosive paint, it brushes onto processed metal plate,
After room temperature curing 1 day, so that it may obtain the excellent coating of antiseptic property in metal surface.
Example 2: using Hummers method is improved, using graphite powder as raw material, graphene oxide dispersion is prepared.Functionalization oxygen
The preparation of graphite alkene, prepares the graphene oxide solution that 100 milliliters of concentration are 0.4% first, 500W ultrasound 30 minutes, then plus
Enter 3.0 grams of para-totuidine, under alkaline condition, stirring, reflux 3 hours at 95 DEG C of temperature filter, cleaned respectively with water and ethyl alcohol
Three to five times, freeze-drying 24 hours to get arrive modified graphene oxide；20mg modified graphene oxide is put into 20ml second two
In alcoholic solution, water bath sonicator disperse 1 hour, later be added 2.0g silica, 0.5g titanium dioxide, 2.0g epoxy resin,
0.16g methacrylic acid magnetic agitation 20 hour, self-emulsifying defoaming agent is added later and is stirred for 30min, stands 1 hour and removes
Bubble obtains the anticorrosive paint that modified graphene oxide content is 1.0%, brushes onto processed metal plate, room temperature curing 1
After it, so that it may obtain the excellent coating of antiseptic property in metal surface.
Claims (10)
1. a kind of functional graphene oxide corrosion-inhibiting coating and its preparation process, key step is the oxidation stone first to preparation
Black alkene (GO) carries out functional modification and obtains functional graphene oxide (P-GO), to improve graphene oxide in organic solvent
Dispersion stabilization, and functional graphene oxide is distributed in organic solvent, secondly inorganic nano-particle (IN) is added
The ultrasonic disperse into graphene oxide dispersion；Then film forming matter is added and stirs certain time, it is modified during which to add surface
Agent, the surface energy to reduce coating, oil paint eliminate bubble present in solution with defoaming agent, stir certain time；Stirring
After stand a period of time, be uniformly applied to using the method for brushing on processed metal plate, room temperature curing one day
The good coating of anti-corrosive properties can be obtained.The mass percentage content of each constituent is as follows in corrosion-inhibiting coating preparation process:
2. according to the method described in claim 1, it is characterized in that carrying out function to graphene oxide using hydro-thermal reflow method
Change be modified, on it be grafted p-phenylenediamine (PPD), γ-methacryloxypropyl trimethoxy silane (MPS), to toluene
Amine etc. obtains functional graphene oxide.
3. according to the method described in claim 1, it is characterized in that functional graphene oxide improves graphene oxide is having
Dispersion stabilization in solvent, content are 0.02~0.2%, are dispersed 0.5~1 hour using water bath sonicator.
4. according to the method described in claim 1, it is characterized in that obtained modified graphene oxide is dissolved in organic solvent,
Organic solvent is methanol, ethylene glycol, N-N- dimethylformamide etc..
5. according to the method described in claim 1, it is characterized in that inorganic nano-particle (IN) uses silica to improve and apply
The roughness of layer, content are 4~12%, and the ultrasonic disperse time is 0.5~2 hour.
6. according to the method described in claim 1, it is characterized in that inorganic nano-particle (IN) also uses titanium dioxide to improve
The hydrophobicity of coating, content are 1~3%, and the ultrasonic disperse time is 0.5~2 hour.
7. according to the method described in claim 1, it is characterized in that film forming matter is mainly polyvinyl butyral (PVB), phenol
Urea formaldehyde, epoxy resin etc., additive amount are 10~4.5%, and mixing time is 12~48 hours.
8. according to the method described in claim 1, it is characterized in that material surface modifying agent uses polydimethylsiloxane prepolymer
Object (PDMS), methacrylic acid, cinnamic acid, polyolefin etc. reduce the surface energy of coating, and content is 4~10%, and mixing time is
12~48 hours.
9. according to the method described in claim 1, it is characterized in that defoaming agent is using higher alcohols, B-457, self-emulsifying defoaming agent etc.
The bubble in solution is removed, additional amount is 0.9~1.9%, and the solution of preparation is stirred 10~30 minutes, is stood after stirring
Deaeration in 10~60 minutes.
10. according to the method described in claim 1, it is characterized in that standing for a period of time, utilizes the side of brushing after stirring
Method is uniformly applied to processed to be obtained to non-corrosive metal (NCM) plate surface on anti-corrosion metal plate after room temperature curing one day
To the good coating of anti-corrosive properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710932359.6A CN109836919B (en) | 2017-09-29 | 2017-09-29 | Functionalized graphene oxide anticorrosive coating and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710932359.6A CN109836919B (en) | 2017-09-29 | 2017-09-29 | Functionalized graphene oxide anticorrosive coating and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109836919A true CN109836919A (en) | 2019-06-04 |
| CN109836919B CN109836919B (en) | 2021-03-26 |
Family
ID=66875855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710932359.6A Active CN109836919B (en) | 2017-09-29 | 2017-09-29 | Functionalized graphene oxide anticorrosive coating and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109836919B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110184596A (en) * | 2019-06-20 | 2019-08-30 | 佛山市众之助新材料科技有限公司 | A method of black phosphating film is covered in metal surface |
| CN110205023A (en) * | 2019-06-21 | 2019-09-06 | 重庆市科学技术研究院 | With hydrophobic, antiseptic property composite Nano coating material and its preparation method and application |
| CN110318069A (en) * | 2019-08-06 | 2019-10-11 | 深圳市康弘环保技术有限公司 | Electrode for electrolysis and preparation method thereof and electrolytic cell |
| CN110713743A (en) * | 2019-10-16 | 2020-01-21 | 广州特种承压设备检测研究院 | Graphene conductive anticorrosive paint for grounding grid and preparation method thereof |
| CN110760252A (en) * | 2019-11-08 | 2020-02-07 | 珠海格力绿色再生资源有限公司 | Novel functional coating and preparation method and application thereof |
| CN110791157A (en) * | 2019-11-18 | 2020-02-14 | 界首市天路包装材料有限公司 | Method for preparing anti-aging and anti-leakage chemical barrel |
| CN111040527A (en) * | 2019-12-31 | 2020-04-21 | 山东华夏神舟新材料有限公司 | Heat-reflecting super-hydrophobic PVDF coating and preparation method thereof |
| CN112676129A (en) * | 2019-10-18 | 2021-04-20 | 天津工业大学 | Graphene anticorrosive coating with layer assembly structure and preparation process thereof |
| CN113755076A (en) * | 2021-09-30 | 2021-12-07 | 南通大学 | Preparation method of aromatic diamine modified graphene oxide epoxy resin coating |
| CN113956746A (en) * | 2021-11-02 | 2022-01-21 | 国科广化韶关新材料研究院 | Water-based epoxy group anticorrosive paint containing composite functionalized modified graphene oxide and preparation method and application thereof |
| CN115926574A (en) * | 2022-12-12 | 2023-04-07 | 南通尔东金属科技有限公司 | Hardware surface anti-corrosion treatment process |
| CN116622270A (en) * | 2023-04-07 | 2023-08-22 | 江南大学 | Modified graphene antirust anticorrosive paint and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105060285A (en) * | 2015-08-26 | 2015-11-18 | 苏州卓伟企业管理咨询有限公司 | Preparing method for modified oxidized graphene |
| CN106380995A (en) * | 2015-07-28 | 2017-02-08 | 魏忠 | Modified graphene anti-corrosion coating layer |
| CN106479313A (en) * | 2016-10-08 | 2017-03-08 | 江苏大使同丰涂料有限公司 | A kind of Graphene anticorrosive paint |
-
2017
- 2017-09-29 CN CN201710932359.6A patent/CN109836919B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380995A (en) * | 2015-07-28 | 2017-02-08 | 魏忠 | Modified graphene anti-corrosion coating layer |
| CN105060285A (en) * | 2015-08-26 | 2015-11-18 | 苏州卓伟企业管理咨询有限公司 | Preparing method for modified oxidized graphene |
| CN106479313A (en) * | 2016-10-08 | 2017-03-08 | 江苏大使同丰涂料有限公司 | A kind of Graphene anticorrosive paint |
Non-Patent Citations (1)
| Title |
|---|
| 李金焕等: "石墨烯/氰酸酯-环氧树脂复合材料的制备和性能", 《复合材料学报》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110184596A (en) * | 2019-06-20 | 2019-08-30 | 佛山市众之助新材料科技有限公司 | A method of black phosphating film is covered in metal surface |
| CN110205023A (en) * | 2019-06-21 | 2019-09-06 | 重庆市科学技术研究院 | With hydrophobic, antiseptic property composite Nano coating material and its preparation method and application |
| CN110318069A (en) * | 2019-08-06 | 2019-10-11 | 深圳市康弘环保技术有限公司 | Electrode for electrolysis and preparation method thereof and electrolytic cell |
| CN110713743A (en) * | 2019-10-16 | 2020-01-21 | 广州特种承压设备检测研究院 | Graphene conductive anticorrosive paint for grounding grid and preparation method thereof |
| CN112676129A (en) * | 2019-10-18 | 2021-04-20 | 天津工业大学 | Graphene anticorrosive coating with layer assembly structure and preparation process thereof |
| CN110760252A (en) * | 2019-11-08 | 2020-02-07 | 珠海格力绿色再生资源有限公司 | Novel functional coating and preparation method and application thereof |
| CN110791157A (en) * | 2019-11-18 | 2020-02-14 | 界首市天路包装材料有限公司 | Method for preparing anti-aging and anti-leakage chemical barrel |
| CN111040527A (en) * | 2019-12-31 | 2020-04-21 | 山东华夏神舟新材料有限公司 | Heat-reflecting super-hydrophobic PVDF coating and preparation method thereof |
| CN113755076A (en) * | 2021-09-30 | 2021-12-07 | 南通大学 | Preparation method of aromatic diamine modified graphene oxide epoxy resin coating |
| CN113956746A (en) * | 2021-11-02 | 2022-01-21 | 国科广化韶关新材料研究院 | Water-based epoxy group anticorrosive paint containing composite functionalized modified graphene oxide and preparation method and application thereof |
| CN113956746B (en) * | 2021-11-02 | 2022-11-29 | 国科广化韶关新材料研究院 | Water-based epoxy group anticorrosive paint containing composite functionalized modified graphene oxide and preparation method and application thereof |
| CN115926574A (en) * | 2022-12-12 | 2023-04-07 | 南通尔东金属科技有限公司 | Hardware surface anti-corrosion treatment process |
| CN116622270A (en) * | 2023-04-07 | 2023-08-22 | 江南大学 | Modified graphene antirust anticorrosive paint and preparation method thereof |
| CN116622270B (en) * | 2023-04-07 | 2024-03-22 | 江南大学 | Modified graphene antirust anticorrosive paint and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109836919B (en) | 2021-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109836919A (en) | A kind of functional graphene oxide corrosion-inhibiting coating and its preparation process | |
| CN104910752B (en) | A kind of polyaniline graphene nano composite anticorrosion coating and preparation method thereof | |
| Hosseinpour et al. | Recent advances and future perspectives for carbon nanostructures reinforced organic coating for anti-corrosion application | |
| CN105238207B (en) | A kind of conductive multifunctional anticorrosive coating of high performance super-amphiphobic and preparation method thereof | |
| CN111100513B (en) | Preparation method of carbon nanotube composite ceramic network modified water-based non-stick coating | |
| Yu et al. | RGO modified ZnAl-LDH as epoxy nanostructure filler: A novel synthetic approach to anticorrosive waterborne coating | |
| CN106398206B (en) | The preparation method of graphene oxide/polyaniline/titanium dioxide nanocomposite and polyaniline nano anticorrosive paint | |
| Zhou et al. | Investigating the effects of g-C3N4/Graphene oxide nanohybrids on corrosion resistance of waterborne epoxy coatings | |
| Wan et al. | Anticorrosive reinforcement of waterborne epoxy coating on Q235 steel using NZ/BNNS nanocomposites | |
| CN111154392B (en) | Modified graphene oxide composite waterborne polyurethane environment-friendly anticorrosive paint | |
| Cui et al. | Functionalized graphene oxide: Carrier for corrosion inhibitor and barrier in waterborne epoxy coatings | |
| CN105478018B (en) | A kind of preparation method of function multi-walled carbon nano-tube blended ultrafiltration membrane | |
| Zhang et al. | TiO2 coated multi-wall carbon nanotube as a corrosion inhibitor for improving the corrosion resistance of BTESPT coatings | |
| Fazli-Shokouhi et al. | Epoxy-matrix polyaniline/p-phenylenediamine-functionalised graphene oxide coatings with dual anti-corrosion and anti-fouling performance | |
| CN113308139B (en) | Two-dimensional nano hybrid composite anticorrosive coating filler and preparation method and application thereof | |
| CN104610780A (en) | Modification method for silicon carbide particles | |
| CN105713426B (en) | A kind of preparation method of marine anticorrosion coating | |
| CN103665973A (en) | Preparation process of inorganic copper imitation coating and process for replacing protective and decorative copper layer of metal surface with inorganic copper imitation coating | |
| CN105647338A (en) | Graphene/epoxy resin composite anticorrosive paint with high isolation and preparation method | |
| CN110527279A (en) | A kind of material and preparation method thereof of high photothermal conversion efficiency high thermal conductivity coefficient | |
| CN115044279A (en) | Two-dimensional polydopamine-reinforced waterborne epoxy composite anticorrosive paint and preparation method and application thereof | |
| Ansari et al. | Study on the protective function of cloisite incorporated silane sol–gel coatings cured at different conditions | |
| CN110713743A (en) | Graphene conductive anticorrosive paint for grounding grid and preparation method thereof | |
| Li et al. | Anticorrosion performance of polyvinyl butyral composite coatings improved by polyaniline-multiwalled carbon nanotubes/poly (methylhydrosiloxane) | |
| CN105111434B (en) | A kind of composite of aniline and graphene, preparation method and applications |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |