CN113943936A - Graphene-silane treating agent, preparation method and application thereof - Google Patents
Graphene-silane treating agent, preparation method and application thereof Download PDFInfo
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- CN113943936A CN113943936A CN202111258648.5A CN202111258648A CN113943936A CN 113943936 A CN113943936 A CN 113943936A CN 202111258648 A CN202111258648 A CN 202111258648A CN 113943936 A CN113943936 A CN 113943936A
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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
- C23C22/34—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
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Abstract
A graphene-silane treating agent is prepared from the following components in percentage by weight: 0.8-1.2% of graphene dispersion liquid, 8.3-10.3% of modified nano silicon dioxide, 2.1-3.1% of 3,3, 3-trifluoropropyltrimethoxysilane, 0.6-0.8% of 3,3, 3-trifluoropropylmethyldimethoxysilane, 3.0-5.0% of fluozirconic acid, 1.0-2.0% of lactic acid, 2.0-3.0% of ammonium citrate and the balance of water. The graphene-silane treating agent is not only suitable for cold-rolled sheets, galvanized sheets, magnesium aluminum sheets and the like, but also suitable for sand-blasted steel sheets, and the formed graphene-silane film has better corrosion resistance than a zinc phosphating film and is a chemical agent for metal surface pretreatment. After a graphene-silane film is formed on the surface of the sand blasting steel plate with the shot blasting derusting grade Sa2.5, the sand blasting steel plate is washed by water and is self-dried and placed for 3 months without rusting.
Description
Technical Field
The invention belongs to the technical field of metal surface treatment, and particularly relates to a graphene-silane treating agent, a preparation method and application thereof.
Background
In the metal surface pretreatment industry, the traditional phosphating treatment has a history of application for nearly one hundred years, and the mature process is approximately as follows: sand blasting → cleaning → pre-degreasing → water washing → surface tone → phosphating → water washing. With the background of gradual implementation of national energy-saving emission-reducing policy and regulation and carbon emission limitation, a large amount of energy is consumed for phosphating treatment, and phosphating solution contains phosphorus and heavy metal elements such as zinc, manganese, nickel and the like and is eliminated by the metal surface pretreatment industry at present. The treatment agent is replaced by a new silane surface treatment agent, a phosphorus-free nano vitrification agent or a silicon-zirconium composite treatment agent which contains environment-friendly materials such as zirconium, titanium, silane coupling agent and the like, and the three agents are energy-saving and environment-friendly, but the performances of the three agents are far from being comparable with the performances of phosphating treatment in the current application situation. For example, the self-drying rust-returning paint can only be used for cold-rolled plates and cannot be used for sand-blasting plates, because the self-drying speed of the sand-blasting plates is low, and the rugged surfaces are easy to store water-storing acid, the self-drying rust-returning of the sand-blasting plates after the silanization treatment is serious, and the corrosion resistance of a silane film, a vitrified film and a silicon-zirconium composite film is greatly reduced compared with that of a phosphating film.
Chinese patent 201710588262.8 discloses a nano ceramic silane composite film conversion agent containing graphene oxide. Consists of 10 to 50 parts of fluozirconic acid, 1 to 20 parts of nitric acid, 1 to 5 parts of silica sol, 1 to 5 parts of complexing agent, 0.1 to 3 parts of silane coupling agent, 0.1 to 1 part of graphene oxide and water which is complemented to 100 parts. According to the invention, silane and silica sol are added into a zirconium salt system for modification to prepare a conversion agent with homogeneous phase stability, an amorphous composite film layer is obtained through zirconium salt silane synergistic treatment, gaps of the film layer can be complemented through graphene oxide, the film layer is more uniform and compact, and the neutral salt spray resistance test of a paint film is also improved to a great extent. In the patent, graphene oxide can only complement film gaps and is not a main constituent of an amorphous composite film; the amorphous composite film obtained in the patent is matched with a paint film to improve the neutral salt spray resistance test to a greater extent, but only the amorphous composite film has poor corrosion resistance, and particularly when the amorphous composite film is matched with a sand blasting test piece, the amorphous composite film is seriously rusted within a short time after being washed and dried by water.
In order to solve the dilemma of the prior metal surface pretreatment industry, a graphene-silane treating agent with better corrosion resistance needs to be developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a graphene-silane treating agent, a preparation method and application thereof.
The technical scheme of the invention is as follows:
a graphene-silane treating agent is prepared from the following components in percentage by weight:
0.8 to 1.2 percent of graphene dispersion liquid,
8.3 to 10.3 percent of modified nano silicon dioxide,
2.1 to 3.1 percent of 3,3, 3-trifluoropropyltrimethoxysilane,
0.6 to 0.8 percent of 3,3, 3-trifluoropropylmethyldimethoxysilane,
3.0 to 5.0 percent of fluozirconic acid,
1.0 to 2.0 percent of lactic acid,
2.0 to 3.0 percent of ammonium citrate,
the balance of water.
The graphene dispersion liquid has the sheet diameter of 50-200nm, the concentration of the dispersion liquid is 0.2-1mg/ml, the solvent is water, and XF020 produced by Jiangsu Xianfeng nanometer material science and technology limited company is preferred.
The preparation method of the modified nano silicon dioxide comprises the following steps:
(1) adding 0.5-1.0 weight part of hydrophobic gas-phase nano silicon dioxide into 15-25 weight parts of toluene, and dispersing to obtain uniform suspension;
(2) then 0.350-0.370 weight part of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH-560) is added into the suspension, ultrasonic mixing is carried out for 5-10min, the mixture reacts for 5-7h in a thermostatic bath at the temperature of 80-95 ℃, and the reaction solution is centrifugally separated at the normal temperature of 10000-15000r/min to obtain the modified nano-silica.
Preferably, the dispersing condition in the step (1) is ultrasonic dispersing for 20-40min by an ultrasonic cleaner at normal temperature.
Preferably, the purity of the silica in step (1) is 99.5 to 99.9%, and the specific surface area (BET): 100-120m2G, the particle diameter is 7-40 nm.
Preferably, the reaction solution in the step (2) is subjected to ultrasonic centrifugation for 5-7 times, and vacuum drying is carried out for 5-10h to obtain the white powder modified nano silicon dioxide.
The dosage of the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane in the step (2) is too small, and the nano silicon dioxide is not completely modified; if the amount of the modified nano silicon dioxide is too large, the modified nano silicon dioxide is unstable to generate white floccule to be settled, and the surface treatment effect of the sand blasting steel plate is influenced.
And (3) replacing the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane in the step (2) with 3,3, 3-trifluoropropyl trimethoxy silane or 3,3, 3-trifluoropropyl methyl dimethoxysilane, so that the prepared modified nano silicon dioxide product is easy to condense and settle, and the surface treatment effect of the sandblasted steel plate is influenced.
The 3,3, 3-trifluoropropyltrimethoxysilane is preferably SCA-F3C3M produced by Nanjing Needer New Material technology Co.
The 3,3, 3-trifluoropropylmethyldimethoxysilane is preferably SCA-F3C3T produced by Nanjing Needer New Material technology Co.
The preparation method of the graphene-silane treating agent comprises the following steps: adding water into a reaction kettle, sequentially adding fluozirconic acid, lactic acid, ammonium citrate, 3,3, 3-trifluoropropyltrimethoxysilane and 3,3, 3-trifluoropropylmethyldimethoxysilane, stirring for 7-10 hours, adding the graphene oxide dispersion liquid and the modified nano-silica, and stirring for 12-15 hours to obtain the graphene-silane treating agent.
The application method of the graphene-silane treating agent comprises the following steps: adding 900-970ml of water into one 1000ml beaker, adding 30-40g of graphene-silane treating agent, testing the pH value of the bath solution to be 2.5-3.5, and if the pH value is lower than 2.5, adding sodium carbonate to adjust the pH value to be 2.5-3.5; if the pH value is more than 3.5, adding a graphene-silane treating agent, and adjusting the pH value to 2.5-3.5.
The formula principle of the graphene-silane treating agent is as follows: when the PH value of the graphene-silane treating agent tank liquor is between 2.5 and 3.5, the graphene oxide, 3, 3-trifluoropropyltrimethoxysilane, 3,3, 3-trifluoropropylmethyldimethoxysilane, modified nano-silica and lactic acid are subjected to polymerization reaction to form a multi-layer cross-linked network structure film; the modified nano silicon dioxide is a film forming main agent and is a film layer framework; 3,3, 3-trifluoropropyltrimethoxysilane and 3,3, 3-trifluoropropylmethyldimethoxysilane have complementarity in the space composition of a film layer, the porosity of the film layer is reduced, the dosage of the 3,3, 3-trifluoropropyltrimethoxysilane is more, and if the dosage of the 3,3, 3-trifluoropropylmethyldimethoxysilane is more than that of the 3,3, 3-trifluoropropyltrimethoxysilane, the porosity of the graphene-silane treatment film layer is increased; when the sand blasting test piece is immersed in the graphene-silane treating agent tank liquor, the PH value at the metal interface is increased, and a multilayer cross-linked network structure film is deposited on the metal surface to form a graphene-silane film; providing an acid environment by the aid of fluorozirconic acid, and filling pores of the graphene-silane film with a zirconium complex generated by hydrolysis; lactic acid provides an acidic environment and also participates in film formation; the ammonium citrate is used for complexing iron or ferrous ions, so that the phenomenon that the film layer is uneven due to interference of metal impurity ions when the multi-layer cross-linked net-shaped structure film is deposited is avoided.
The invention also includes the application of the graphene-silane treating agent in treating the sand-blasting steel plate.
The invention has the following beneficial effects: the graphene-silane treating agent is not only suitable for cold-rolled sheets, galvanized sheets, magnesium aluminum sheets and the like, but also suitable for sand-blasted steel sheets, and the formed graphene-silane film has better corrosion resistance than a zinc-based phosphating film and is a chemical agent for metal surface pretreatment. After the surface of the sand blasting steel plate with the rust removal grade of Sa2.5 is sprayed, a graphene-silane film is formed, and the sand blasting steel plate is washed by water, dried by air and placed for 3 months without rusting.
Detailed Description
Modified nano-silica A:
(1) adding 0.5 weight part of hydrophobic gas-phase nano-silica into 15 weight parts of toluene, and ultrasonically dispersing for 30min at normal temperature by using an ultrasonic cleaner (300W) to obtain uniform suspension;
(2) and then 0.350 part by weight of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH-560) is added into the suspension, ultrasonic mixing is carried out for 7min, the mixture reacts for 6h in a thermostatic bath at the temperature of 85 ℃, and the reaction solution is centrifugally separated at the normal temperature of 12000r/min to obtain the modified nano-silicon dioxide.
The purity of the silicon dioxide in the step (1) is 99.5-99.9%, and the specific surface area (BET): 100-120m2G, the particle diameter is 7-40 nm.
And (3) ultrasonically centrifuging the reaction liquid in the step (2) for 6 times, and drying in vacuum for 8 hours to obtain white powder modified nano silicon dioxide.
Modified nano-silica B:
(1) adding 1.0 weight part of hydrophobic gas-phase nano-silica into 25 weight parts of toluene, and ultrasonically dispersing for 30min at normal temperature by using an ultrasonic cleaner (300W) to obtain a uniform suspension;
(2) and then 0.370 part by weight of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH-560) is added into the suspension, ultrasonic mixing is carried out for 7min, the mixture reacts for 5h in a constant temperature groove at the temperature of 90 ℃, and the reaction solution is centrifugally separated at the normal temperature of 15000r/min to obtain the modified nano silicon dioxide.
The purity of the silicon dioxide in the step (1) is 99.5-99.9%, and the specific surface area (BET): 100-120m2G, the particle diameter is 7-40 nm.
And (3) ultrasonically centrifuging the reaction liquid in the step (2) for 7 times, and performing vacuum drying for 6 hours to obtain white powder modified nano silicon dioxide.
The inventive examples and comparative examples are shown in Table 1 (percentage content), wherein comparative example 1 employs the corresponding unmodified hydrophobic fumed nanosilica in the preparation method of modified nanosilica B, the rest being the same as example 4; the amount of 3,3, 3-trifluoropropyltrimethoxysilane used in comparative example 2 was 3.9%, which was the sum of the amount of 3,3, 3-trifluoropropyltrimethoxysilane and the amount of 3,3, 3-trifluoropropylmethyldimethoxysilane used in example 4, and 3,3, 3-trifluoropropylmethyldimethoxysilane was not contained; the amount of 3,3, 3-trifluoropropylmethyldimethoxysilane used in comparative example 3 was 3.9%, which was the sum of the amount of 3,3, 3-trifluoropropyltrimethoxysilane and the amount of 3,3, 3-trifluoropropylmethyldimethoxysilane used in example 4, and 3,3, 3-trifluoropropyltrimethoxysilane was not included; comparative example 4 was the same as example 2 except that lactic acid was replaced with the same amount of nitric acid.
TABLE 1
The preparation method of the graphene-silane treating agent described in the examples is as follows:
adding water into a reaction kettle, sequentially adding fluozirconic acid, lactic acid, ammonium citrate, 3,3, 3-trifluoropropyltrimethoxysilane and 3,3, 3-trifluoropropylmethyldimethoxysilane, stirring for 8 hours, adding a graphene oxide dispersion liquid and modified nano-silica, and stirring for 15 hours to obtain the graphene-silane treating agent.
The graphene-silane treating agent is used in the following method:
adding 970ml of water into one 1000ml beaker, adding 30g of graphene-silane treating agent, testing the pH value of the bath solution to be 2.5-3.5, and adding sodium carbonate to adjust the pH value to be 2.5-3.5 if the pH value is lower than 2.5; if the pH value is more than 3.5, adding a graphene-silane treating agent, and adjusting the pH value to 2.5-3.5. And (3) putting the sand blasting steel plate into the solution for 5 minutes, then taking out, washing the sand blasting steel plate with clear water, drying the sand blasting steel plate, and forming the graphene-silane composite film on the surface of the sand blasting steel plate.
The performance of the graphene-silane film formed on the metal surface by the graphene-silane treatment agent is shown in tables 2-3, and the data in table 2 is the test result after the graphene-silane film is formed on the surface of the sand blasting steel plate with the shot blasting derusting grade Sa2.5.
TABLE 2
TABLE 3
Claims (9)
1. The graphene-silane treating agent is characterized by being prepared from the following components in percentage by weight: 0.8-1.2% of graphene dispersion liquid, 8.3-10.3% of modified nano silicon dioxide, 2.1-3.1% of 3,3, 3-trifluoropropyltrimethoxysilane, 0.6-0.8% of 3,3, 3-trifluoropropylmethyldimethoxysilane, 3.0-5.0% of fluozirconic acid, 1.0-2.0% of lactic acid, 2.0-3.0% of ammonium citrate and the balance of water.
2. The graphene-silane treatment agent according to claim 1, wherein the graphene dispersion has a sheet diameter of 50 to 200nm, a dispersion concentration of 0.2 to 1mg/ml, and a solvent of water.
3. The graphene-silane treatment agent according to claim 1, wherein the modified nano-silica is prepared by the following method:
(1) adding 0.5-1.0 weight part of hydrophobic gas-phase nano silicon dioxide into 15-25 weight parts of toluene, and dispersing to obtain uniform suspension;
(2) then 0.350-0.370 weight part of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is added into the suspension, ultrasonic mixing is carried out for 5-10min, the mixture reacts in a thermostatic bath at the temperature of 80-95 ℃ for 5-7h, and 10000/15000 r/min centrifugal separation is carried out on the reaction liquid at normal temperature to obtain the modified nano silicon dioxide.
4. The graphene-silane treatment agent according to claim 3, wherein the specific surface area of the silica in step (1) is 100-120m2G, the particle diameter is 7-40 nm.
5. The graphene-silane treatment agent according to claim 3, wherein the dispersion condition in the step (1) is ultrasonic dispersion for 20-40min by an ultrasonic cleaner at normal temperature.
6. The graphene-silane treatment agent according to claim 3, wherein the reaction solution in the step (2) is subjected to ultrasonic centrifugation for 5-7 times and vacuum drying for 5-10 hours.
7. The graphene-silane treatment agent according to claim 1, wherein the graphene-silane treatment agent is prepared from the following components in percentage by weight: 1.2% of graphene dispersion liquid, 10.1% of modified nano silicon dioxide, 3.1% of 3,3, 3-trifluoropropyltrimethoxysilane, 0.8% of 3,3, 3-trifluoropropylmethyldimethoxysilane, 4.9% of fluozirconate, 1.9% of lactic acid, 2.9% of ammonium citrate and the balance of water.
8. The method for preparing the graphene-silane treating agent according to claim 1, comprising the following steps in sequence: adding water into a reaction kettle, sequentially adding fluozirconic acid, lactic acid, ammonium citrate, 3,3, 3-trifluoropropyltrimethoxysilane and 3,3, 3-trifluoropropylmethyldimethoxysilane, stirring for 7-10 hours, adding the graphene dispersion liquid and the modified nano-silica, and stirring for 12-15 hours to obtain the graphene-silane treating agent.
9. Use of the graphene-silane treatment agent according to claim 1 for treating sandblasted steel sheets.
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| CN202111258648.5A CN113943936B (en) | 2021-10-28 | 2021-10-28 | Graphene-silane treating agent, preparation method and application thereof |
| PCT/CN2021/127833 WO2023070645A1 (en) | 2021-10-28 | 2021-11-01 | Graphene-silane treating agent and preparation method therefor and application thereof |
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| 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 |
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| US9273399B2 (en) * | 2013-03-15 | 2016-03-01 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a battery electrode |
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| CN106048575A (en) * | 2016-07-20 | 2016-10-26 | 湖南金裕环保科技有限公司 | Graphene metal surface treatment agent, preparation method and application |
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| CN107142472A (en) * | 2017-05-27 | 2017-09-08 | 湖南金裕环保科技有限公司 | Graphene nano film agent and preparation method thereof |
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| 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 |
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