CN108707886A - A kind of preparation method of graphene oxide enhancing silane film - Google Patents
A kind of preparation method of graphene oxide enhancing silane film Download PDFInfo
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- CN108707886A CN108707886A CN201810615470.7A CN201810615470A CN108707886A CN 108707886 A CN108707886 A CN 108707886A CN 201810615470 A CN201810615470 A CN 201810615470A CN 108707886 A CN108707886 A CN 108707886A
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- silane
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- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
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- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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Abstract
The present invention relates to the preparation methods that a kind of graphene oxide enhances silane film, first will double-[ γ-（Triethoxysilicane）Propyl ]-tetrasulfide silane BTESP mix to volume fraction be 80-85% ethanol solution in mix and water bath with thermostatic control in be hydrolyzed, graphene oxide is added into the solution of silane after hydrolysis, a concentration of 50 ~ the 100mg/L for making graphene oxide, finally cures 40Cr steel matrix in solution of silane.Preparation method of the present invention is simple, and step is easily operated, entire process environmental protection and energy saving, adaptable, and graphene oxide is adulterated in solution of silane can hinder diffusion of the corrosive medium in silane film, can improve the anti-corrosion stability of silane film.
Description
Technical field
The present invention relates to the preparation methods that a kind of graphene oxide enhances silane film, belong to membrane preparation technology field.
Background technology
Silanized surface treatment technology be using silane be primary raw material metal surface deposit silane film a kind of surface at
Manage new technology.Silanized surface treatment technology has the following advantages：It is not phosphorous without harmful heavy metal ions；In silanization process
Do not generate sediment, processing time is short, control simplicity；Adhesive force of the coating to base material can be effectively improved.Silanization treatment is expected to take
The single component for for traditional phosphorization treatment technology, having a extensive future in field of surface treatment, but being prepared using conventional method
Silane film thinner thickness, consistency it is relatively low, be commonly present stomata and micro-crack etc., it is anti-to limit corrosion that it is used alone for a long time
Shield ability.
Graphene oxide has fine and close two-dimension single layer planar structure and excellent both thermally and chemically stability, has made
It is applied to metal surface for diffusion barrier and antioxidant coating.Meanwhile the single layer planar structure and nanometer of graphene oxide two-dimensional
Grade thickness, than the transverse and longitudinal ratio and more high-specific surface area that carbon nanotube has bigger, these features are in enhancing silane film dynamic performance
Aspect plays an important roll, therefore by adding graphene oxide in silane film, hinders expansion of the corrosive medium in silane film
It dissipates, to achieve the purpose that improve the anti-corrosion stability of silane film.
During preparing silane film, the side that processing is passivated to metallic matrix reaches very much, and there are commonly dip-coating liftings
Method, dip coating, spin-coating method, electrophoresis, wherein dip coating are easy to operate due to simple for process, are not limited by space enrironment
System, the production being more suitable in industry.
Invention content
It is insufficient existing for the single silanization treatment of tradition the purpose of the invention is to overcome, a kind of graphene oxide is provided
Enhance the preparation method of silane film, this method hydrolysis time is short, and production efficiency is high, and environmental protection and energy saving, safety is good, production cost
Low, technological operation is simple, good product performance.
The present invention adopts the following technical scheme that：A kind of preparation method of graphene oxide enhancing silane film, including walk as follows
Suddenly：
(1) double-[ are taken;γ-(triethoxysilicane) Bing Jis ]Tetrasulfide silane BTESP is mixed to ethyl alcohol
The solution of silane of 3~5vol% is formed in solution, the volume fraction of the ethanol solution is 80-85%, is used
Magnetic agitation mixing；
(2) it uses glacial acetic acid and ammonium hydroxide to adjust solution of silane pH value to 4.0~4.5, BTESP is made to carry out water in water bath with thermostatic control
Solution；
(3) graphene oxide powder is added into the solution of silane after hydrolysis, make graphene oxide a concentration of 50~
100mg/L, ultrasonic disperse 3-40min；
(4) the 40Cr steel metal matrixes after acetone is cleaned by ultrasonic are placed in 3~3.5% sodium hydroxide solutions and are impregnated
20~30s, taking-up deionized water are rinsed and are dried up for use；
(5) metallic matrix is placed in the solution of silane prepared after being passivated 40~90s and takes out and dries up；
(6) metallic matrix after drying is placed in the air dry oven that temperature is 100~140 DEG C the 30- that is heating and curing
40min obtains graphene oxide enhancing silane film.
Further, the temperature of the water bath with thermostatic control in the step (2) is 30~35 DEG C, and hydrolysis time is 20~30h.
Further, the graphene oxide lateral dimension is 0.5~10 μm.
Further, the frequency of ultrasonic disperse is 20-40K Hz in the step (3).
Beneficial effects of the present invention are：Preparation method of the present invention is simple, and step is easily operated, entire process environmental protection section
Can, adaptable, doping graphene oxide can hinder diffusion of the corrosive medium in silane film, Neng Gouti in solution of silane
The anti-corrosion stability of high silane film.
Specific implementation mode
Below in conjunction with specific embodiment, the invention will be further described.
Double-[ in the present invention;γ-(triethoxysilicane) Bing Jis ]It is purchased from Jing Zhou Jiang-Han Area fine chemistry industry outside tetrasulfide silane
Co., Ltd, graphene oxide are purchased from Shanghai carbon source Hui Gu new materials Science and Technology Ltd. outside.
Comparative example one：
According to BTESPT concentration 5vol%, the volume ratio of water and ethyl alcohol is 20:80, magnetic agitation 10 minutes, the pH of solution
4.0 are adjusted to glacial acetic acid and ammonium hydroxide, is hydrolyzed 24 hours in the thermostat water bath that temperature is 35 DEG C, by 40Cr matrix sand paper
It is cleaned by ultrasonic with acetone after polishing, is rinsed and dried up with deionized water, immersed in 3.5% sodium hydroxide solution 20 seconds, is taken out
It is rinsed and is dried up with deionized water, be put into the solution of silane prepared and be passivated 40 seconds, take out sample and dried up, be placed on 100
DEG C air dry oven in cure 30 minutes and obtain finished product.
Embodiment one：
According to BTESPT concentration 5vol%, the volume ratio of water and ethyl alcohol is 20:The pH of 80, magnetic agitation 10min, solution are used
Glacial acetic acid and ammonium hydroxide are adjusted to 4.0, are hydrolyzed in the thermostat water bath that temperature is 35 DEG C for 24 hours, graphene oxide powder is added, makes
Graphene oxide content is 50mg/L, and ultrasonic disperse 20min in solution after must hydrolyzing, and is used after 40Cr matrixes are polished with sand paper
Acetone is cleaned by ultrasonic, and is rinsed and is dried up with deionized water, and 20s in 3.5% sodium hydroxide solution, taking-up deionized water are immersed
It rinses and dries up, be put into the solution of silane prepared and be passivated 40s, take out sample and dry up, be placed on 100 DEG C of forced air drying
Cure 30min in case and obtains finished product.
Embodiment two：
According to BTESPT concentration 4.5vol%, the volume ratio of water and ethyl alcohol is 15:85, magnetic agitation 10min, the pH of solution
4.3 are adjusted to glacial acetic acid and ammonium hydroxide, 30h is hydrolyzed in the thermostat water bath that temperature is 30 DEG C, graphene oxide powder is added,
So that graphene oxide content is 120mg/L in solution after hydrolysis, and ultrasonic disperse 20min, 40Cr matrixes are polished with sand paper
It is cleaned by ultrasonic afterwards with acetone, is rinsed and dried up with deionized water, immerses 30s in 3% sodium hydroxide solution, taking-up deionization
Water is rinsed and is dried up, and is put into the solution of silane prepared and is passivated 60s, is taken out sample and is dried up, and it is dry to be placed on 140 DEG C of air blast
Cure 40min in dry case and obtains finished product.
Embodiment three：
According to BTESPT concentration 3vol%, the volume ratio of water and ethyl alcohol is 20:The pH of 80, magnetic agitation 10min, solution are used
Glacial acetic acid and ammonium hydroxide are adjusted to 4.0, are hydrolyzed in the thermostat water bath that temperature is 35 DEG C for 24 hours, graphene oxide powder is added, makes
Graphene oxide content is 50mg/L, and ultrasonic disperse 20min in solution after must hydrolyzing, and is used after 40Cr matrixes are polished with sand paper
Acetone is cleaned by ultrasonic, and is rinsed and is dried up with deionized water, and 20s in 3.5% sodium hydroxide solution, taking-up deionized water are immersed
It rinses and dries up, be put into the solution of silane prepared and be passivated 40s, take out sample and dry up, be placed on 100 DEG C of forced air drying
Cure 30min in case and obtains finished product.
Comparative example one, 40Cr steel matrix and embodiment two are compared.
Three kinds of samples are subjected to three groups of copper sulphate titration experiments respectively, results are averaged as table 1 tests solution composition ginseng
According to QB/T 3824-1999, including pure 40 milliliters of the copper sulphate of 0.5mol/L chemistry, 10% 20 milliliters of chemical pure sodium chloride and
0.8 milliliter of 0.1mol/L chemistry pure hydrochloric acid.There is rosiness spot in the timing since copper sulphate drips to specimen surface, specimen surface
Until, for the sample copper corrosion of the resistance to sulfuric acid time.
According to copper sulphate titration experiments can be seen that graphene oxide content be 50mg/L when, silane film obtained is resistance to
Corrosive effect is best, and apparent reinforcement has been obtained compared to its corrosion resistance of single silane film in comparative example.
1 copper sulphate titration experiments result of table
Same three kinds of samples carry out polarization curve test, and part of three kinds of samples in addition to testing film surface is all used
704 silica gel uniformly smear encapsulation to ensure to insulate, and impregnate sample 1 hour in 3.5% sodium chloride solution before test, by sample
As working electrode, saturated calomel electrode is reference electrode, and using platinum electrode as auxiliary electrode, solution is 3.5% sodium chloride solution.
Scanning range is -0.7~-0.3, sweep speed 2mV/s, test result such as table 2.
2 various sample parameters of electrochemical corrosion of table
As can be seen from Figure 1 the anodic polarization curves of two kinds of silane film samples and cathodic polarization curve are in untreated examination
The lower section of sample, this explanation are suppressed by the sample anode and cathode reaction of silanization treatment, and silane film effectively acts as
The effect for obstructing corrosive medium, improves the corrosion resisting property of 40Cr matrixes.In addition, can be derived that from table 2, graphite oxide is added
Silane film its corrosion potential of mixing of alkene is increased compared to single silane film, and corrosion current density declines nearly two quantity
Grade, this illustrates that its corrosion resistance of the silane film of doping graphene oxide is significantly improved compared to single silane film.
Contact angle experiments are carried out for three kinds of samples, contact angle is to show that liquid can be most intuitive in Wettability of Solid Surface
One of method is taken pictures after dropping liquid 5s at room temperature with deionized water, and various sample contact angle image such as Fig. 2, Fig. 3, figure are formed
4, experimental result such as table 3.
Fig. 2 be deionized water untreated matrix surface image, contact angle size be 57.41 °, wetability compared with
It is good.Fig. 3 is the specimen surface deionized water image that comparative example one is prepared, and contact angle size is 79.77 °.Fig. 4 is to implement
The specimen surface deionized water image that example one is prepared, contact angle size are 87.41 °.
3 various sample contact angle experiments result of table
As can be seen that untreated samples surface wettability is preferable from the contact angle size of three width figures, belong to water-wetted surface,
And the surface contact angle Jing Guo silane treatment is larger, close to hydrophobic surface, and adulterates the silane film of graphene oxide its contact angle
It is greater than the contact angle of single silane film, the hydrophobicity on surface is stronger.
Claims (4)
1. a kind of preparation method of graphene oxide enhancing silane film, it is characterized in that：Include the following steps：
（1）Take double-[ γ-（Triethoxysilicane）Propyl ]-tetrasulfide silane BTESP mix into ethanol solution formed 3 ~
The volume fraction of the solution of silane of 5vol%, the ethanol solution is 80-85%, with magnetic agitation mixing；
（2）Solution of silane pH value is adjusted to 4.0 ~ 4.5 with glacial acetic acid and ammonium hydroxide, and BTESP is made to be hydrolyzed in water bath with thermostatic control；
（3）Graphene oxide powder is added into the solution of silane after hydrolysis, makes a concentration of 50 ~ 100mg/L of graphene oxide,
Ultrasonic disperse 3-40min；
（4）By the 40Cr steel metal matrixes after acetone is cleaned by ultrasonic be placed in 3 ~ 3.5% sodium hydroxide solutions impregnate 20 ~
30s, taking-up deionized water are rinsed and are dried up for use；
（5）Metallic matrix is placed in the solution of silane prepared after being passivated 40 ~ 90s and takes out and dry up；
（6）Metallic matrix after drying is placed in the air dry oven that temperature is 100 ~ 140 DEG C the 30-40min that is heating and curing, is obtained
Enhance silane film to graphene oxide.
2. the preparation method of graphene oxide enhancing silane film as described in claim 1, it is characterized in that：The step（2）In
Water bath with thermostatic control temperature be 30 ~ 35 DEG C, hydrolysis time be 20 ~ 30h.
3. the preparation method of graphene oxide enhancing silane film as described in claim 1, it is characterized in that：The graphene oxide
Lateral dimension be 0.5 ~ 10 μm.
4. the preparation method of graphene oxide enhancing silane film as described in claim 1, it is characterized in that：The step（3）In
The frequency of ultrasonic disperse is 20-40K Hz.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627979A (en) * | 2018-12-16 | 2019-04-16 | 桂林理工大学 | A method of graphene/silicon alkane laminated film is prepared in aluminum alloy surface |
| CN110373698A (en) * | 2019-08-14 | 2019-10-25 | 桂林理工大学 | A method of differential arc oxidation/graphene/silicon alkane laminated film is prepared in aluminum alloy surface |
| CN110396709A (en) * | 2019-08-14 | 2019-11-01 | 桂林理工大学 | A method of differential arc oxidation/graphene oxide/silane laminated film is prepared in aluminum alloy surface |
| CN111455363A (en) * | 2020-04-07 | 2020-07-28 | 西安石油大学 | Passivation solution and preparation method and application thereof |
| CN112126264A (en) * | 2020-09-15 | 2020-12-25 | 常州大学 | Magnesium alloy anticorrosion and wear-resistant coating composition and use method thereof |
-
2018
- 2018-06-14 CN CN201810615470.7A patent/CN108707886A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 吴超云等: "金属表面硅烷防护膜层的研究进展", 《表面技术》 * |
| 张振岳: "不锈钢表面硅烷/氧化石墨烯膜层的制备及其腐蚀性能研究", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627979A (en) * | 2018-12-16 | 2019-04-16 | 桂林理工大学 | A method of graphene/silicon alkane laminated film is prepared in aluminum alloy surface |
| CN109627979B (en) * | 2018-12-16 | 2021-04-09 | 桂林理工大学 | Method for preparing graphene/silane composite film on surface of aluminum alloy |
| CN110373698A (en) * | 2019-08-14 | 2019-10-25 | 桂林理工大学 | A method of differential arc oxidation/graphene/silicon alkane laminated film is prepared in aluminum alloy surface |
| CN110396709A (en) * | 2019-08-14 | 2019-11-01 | 桂林理工大学 | A method of differential arc oxidation/graphene oxide/silane laminated film is prepared in aluminum alloy surface |
| CN111455363A (en) * | 2020-04-07 | 2020-07-28 | 西安石油大学 | Passivation solution and preparation method and application thereof |
| CN112126264A (en) * | 2020-09-15 | 2020-12-25 | 常州大学 | Magnesium alloy anticorrosion and wear-resistant coating composition and use method thereof |
| CN112126264B (en) * | 2020-09-15 | 2021-12-21 | 常州大学 | Magnesium alloy anticorrosion and wear-resistant coating composition and use method thereof |
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Application publication date: 20181026 |