CN112409834A - Preparation of graphene-shaped ceramic oxide nanosheet pigment filler for anticorrosive paint - Google Patents
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Abstract
Preparation of graphene-shaped ceramic oxide nanosheet pigment filler for anticorrosive paint, belonging to the field of anticorrosive paint. Adsorbing the ceramic oxide precursor to graphene oxide with negative electricity, placing the graphene oxide precursor in deionized water, fully stirring and mixing, then heating in a beaker in a water bath, and removing the graphene oxide through high-temperature calcination treatment to obtain the graphene-shaped ceramic oxide nanosheet. The paint prepared by the pigment and filler has excellent corrosion resistance, good high-temperature stability and chemical stability, and can meet the requirements of practical application. The graphene-like pigment and filler material has the characteristics of excellent strength, hardness, insulativity, corrosion resistance and the like, and is environment-friendly, low in preparation cost and wide in application prospect.
Description
Technical Field
The invention belongs to the field of anticorrosive coatings, and particularly relates to a graphene-shaped ceramic oxide nanosheet pigment filler which is applied to an anticorrosive coating.
Background
The ceramic oxide has the characteristics of insulativity, strong mechanical property, chemical stability and the like, and is a good pigment filler. According to the nature of the pigment and filler, the addition of the ceramic oxide can enhance the elastic rigidity, flame retardance, wear resistance, optical characteristics, electrical performance, thermal performance and other properties of the polymer coating. In addition, the ceramic oxide improves the barrier properties of the polymeric coating to corrosive media by compensating for porosity of the coating that occurs during curing. Ceramic oxides are typically added to the coating in the form of nanoparticles, but nanoparticles tend to agglomerate inside the coating, which limits the role of the ceramic oxide filler in the coating. Compared with nanoparticles, the two-dimensional filler has a wide application prospect in coatings, such as graphene. Due to the fact that the specific surface area of the graphene is large, the corrosion path of the coating can be effectively prolonged through the graphene, and therefore the corrosion resistance of the coating is improved.
The graphene anti-corrosion coating has a fatal defect, and since graphene has high conductivity, when the coating is damaged, microcurrent corrosion easily occurs at the position where the graphene is in contact with the coating, so that the corrosion is aggravated. Therefore, the graphene-shaped ceramic oxide nanosheet pigment and filler for the anticorrosive coating is provided, the corrosion path of the coating is effectively prolonged by integrating the advantages of the ceramic oxide and the graphene, and the generation of micro-current corrosion after the coating is damaged is avoided, so that the pigment and filler has very important significance.
Disclosure of Invention
The invention aims to provide a graphene-shaped ceramic oxide nanosheet, which overcomes the defects in the prior art.
The invention also aims to provide a pigment filler of the anticorrosive coating, wherein the pigment filler comprises the graphene-shaped ceramic oxide nanosheet, namely, the morphology of the ceramic oxide is regulated and controlled to be of a graphene-like structure.
The graphene-shaped ceramic oxide nanosheet pigment and filler is a ceramic oxide material with a graphene lamellar structure. The ceramic oxide is metal oxide, and is selected from zirconia, alumina, silica, magnesia, and calcium oxide.
The preparation method comprises the following steps:
(1) preparing a graphene oxide/ceramic oxide precursor composite:
ultrasonically dispersing graphene oxide in water to prepare 0.001-10g/ml graphene oxide turbid liquid; adding a ceramic oxide precursor, adjusting the pH value to 7-14, stirring for 0.5-48h, after the reaction is finished, centrifugally cleaning, and freeze-drying to obtain a graphene oxide/ceramic oxide precursor compound; the mass ratio of the graphene oxide to the ceramic oxide precursor is 1:1-30, preferably 1: 10-20;
(2) preparing graphene-like ceramic oxide nanosheets:
putting the graphene oxide/ceramic oxide precursor composite prepared in the step (1) into a muffle furnace, reacting at the temperature of 450-800 ℃ for 1-24h, and cooling to room temperature after the reaction is finished to obtain graphene-shaped ceramic oxide nanosheets;
(3) preparing a modified graphene-shaped ceramic oxide nanosheet:
dispersing the graphene-shaped ceramic oxide nanosheets reacted in the step (2) in ethanol to prepare 0.001-1g/ml of ceramic oxide turbid liquid; adding a silane coupling agent, reacting at 60-90 ℃ for 0.5-48h, adding 1-30mL of water into the mixture after the reaction is finished, stirring for 0.5-48h, washing, and freeze-drying to obtain the modified graphene-shaped ceramic oxide nanosheet. The mass ratio of the graphene-shaped ceramic oxide nanosheets to the silane coupling agent is 1:1-40, preferably 1: 10-25.
The precursor of the metal oxide adopts one of zirconium oxychloride octahydrate, aluminum sulfate, silicon tetrachloride, magnesium sulfate and calcium dichloride.
According to the invention, a silane coupling agent is used for modifying graphene-shaped ceramic oxide nanosheets, and is selected from one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 3- (methacryloyloxy) propyltrimethoxysilane;
the graphene-like pigment filler disclosed by the invention is a graphene-like structure formed by regulating and controlling the appearance of a ceramic oxide, and is used in the field of anticorrosive coatings. By integrating the advantages of the ceramic oxide and the graphene, the corrosion resistance of the polymer coating is improved, and the generation of micro-current corrosion after the coating is damaged is effectively avoided.
The paint is an epoxy paint added with graphene-shaped pigment and filler. The preparation method comprises the following steps: adding the graphene-shaped ceramic oxide nanosheet pigment filler into an organic solvent (preferably n-butyl alcohol), then adding a film forming substance and an auxiliary agent, uniformly mixing, and coating on a metal substrate; wherein the mass ratio of the graphene-shaped ceramic oxide nanosheet pigment filler to the organic solvent is 1: 5-20.
The mass ratio of the film forming material to the pigment and filler is 10:0.01-0.5, and the mass ratio of the film forming material to the pigment and filler is preferably 10: 0.1-0.2.
The film-forming substance provided by the invention is epoxy resin E44 or epoxy resin E51.
The metal substrate for protection of the anticorrosive paint provided by the invention is an aluminum sheet, a copper sheet or a tinplate.
Compared with the prior art, the invention has the following advantages:
1) the method provided by the invention is simple and easy to operate, good in repeatability, strong in controllability and easy to popularize in a large range.
2) The preparation method of the pigment and filler provided by the invention adopts a template method, forms the graphene-shaped ceramic oxide through electrostatic adsorption, and can effectively prolong the corrosion path of the coating.
3) The pigment and filler material prepared by the invention has the characteristics of excellent strength, hardness, insulativity, corrosion resistance and the like, and is environment-friendly and low in preparation cost.
4) The paint provided by the invention has excellent corrosion resistance, good high-temperature stability and chemical stability, and can meet the requirements of practical application.
5) The coating provided by the invention has the advantages of low preparation cost, long service life and wide application range.
Drawings
FIG. 1 is a scanning electron microscope image of graphene-like pigment filler in the example.
FIG. 2 is a transmission electron microscope image of graphene-like pigment/filler in the example.
FIG. 3 is a Nyquist plot of the coatings in the examples.
The invention is further illustrated by the following figures and examples.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
The coating taking the zirconium oxide nanosheet as the pigment and filler is prepared according to the following steps:
(1) preparing a graphene oxide/zirconium hydroxide precursor compound: ultrasonically dispersing 30mg of graphene oxide in 20mL of water to prepare 1.5g/mL of graphene oxide turbid liquid, adding 470.79mg of zirconium oxychloride octahydrate under the stirring condition, adjusting the pH of the solution to 8 by using 0.1mol/L of sodium hydroxide, stirring for 3 hours, after the reaction is finished, centrifugally cleaning, and freeze-drying to obtain the graphene oxide/zirconium hydroxide precursor compound.
(2) Preparing graphene-like zirconium oxide nanosheets: and (2) putting the graphene oxide/zirconium hydroxide precursor compound prepared in the step (1) into a muffle furnace, reacting for 2h at 700 ℃, cooling to room temperature after the reaction is finished, and obtaining the graphene-shaped zirconium oxide nanosheet, wherein a scanning electron microscope image and a transmission electron microscope image of the prepared material are respectively shown in fig. 1 and fig. 2.
(3) Preparing a modified graphene-shaped zirconium oxide nanosheet: dispersing the graphene-shaped zirconium oxide nanosheets reacted in the step (2) in 50mL of ethanol to prepare 0.005g/mL of ceramic oxide turbid liquid, adding 5g of silane coupling agent, reacting at 80 ℃ for 8h, adding 15mL of water into the mixture after the reaction is finished, stirring for 12h, washing, and freeze-drying to obtain the modified graphene-shaped zirconium oxide nanosheets.
(4) Preparing a coating with zirconium oxide nano-sheets as pigments and fillers: dispersing the modified graphene-shaped zirconium oxide nanosheets reacted in the step (3) into n-butanol (the mass ratio of the zirconium oxide nanosheets to the n-butanol is 1: 5-20). Then adding epoxy resin, stirring uniformly (the mass ratio of the zirconia nano-sheets to the epoxy resin is 1:100), finally adding the mixture into polyamide 650 (the mass ratio of the zirconia nano-sheets to the polyamide 650 is 1:20), and mixing uniformly. The Nyquist plot of the coating is shown in fig. 3, which is prepared by knife coating the viscous mixture onto tinplate.
Through characterization, the nanosheet obtained in the embodiment has a graphene-like structure, and after the nanosheet is applied to a coating, the coating has better corrosion resistance.
Example 2
The coating taking the alumina nano-sheet as the pigment and filler is prepared according to the following steps:
(1) preparing a graphene oxide/aluminum hydroxide precursor compound: ultrasonically dispersing 30mg of graphene oxide in 20mL of water to prepare 1.5g/mL of graphene oxide turbid liquid, adding 487.57mg of aluminum sulfate under the stirring condition, adjusting the pH value of the solution to 7 by using 0.1mol/L of sodium hydroxide, stirring for 3 hours, centrifugally cleaning after the reaction is finished, and freeze-drying to obtain the graphene oxide/aluminum hydroxide precursor compound.
(2) Preparing graphene-like aluminum oxide nanosheets: and (2) putting the graphene oxide/aluminum hydroxide precursor compound prepared in the step (1) into a muffle furnace, reacting for 2h at 600 ℃, and cooling to room temperature after the reaction is finished to obtain the graphene-shaped aluminum oxide nanosheet.
(3) Preparing a modified graphene-like alumina nanosheet: dispersing the graphene-shaped alumina nanosheets reacted in the step (2) in 50mL of ethanol to prepare 0.005g/mL of ceramic oxide turbid liquid, adding 5g of silane coupling agent, reacting at 80 ℃ for 8h, adding 15mL of water into the mixture after the reaction is finished, stirring for 12h, washing, and freeze-drying to obtain the modified graphene-shaped alumina nanosheets.
(4) Preparing a coating with an alumina nano sheet as a pigment and filler: dispersing the modified graphene-shaped alumina nano sheet reacted in the step (3) into n-butanol (the mass ratio of the alumina nano sheet to the n-butanol is 1: 5-20). Then adding epoxy resin, stirring uniformly (the mass ratio of the aluminum oxide nano sheet to the epoxy resin is 1:100), finally adding the mixture into polyamide 650 (the mass ratio of the aluminum oxide nano sheet to the polyamide 650 is 1:20), and mixing uniformly. The viscous mixture was spread evenly on a tinplate by knife coating.
Example 3
The coating taking the silicon oxide nanosheet as the pigment and filler is prepared according to the following steps:
(1) preparing a graphene oxide/silicon hydroxide precursor compound: ultrasonically dispersing 30mg of graphene oxide in 20mL of water to prepare 1.5g/mL of graphene oxide turbid liquid, adding 495.56mg of silicon tetrachloride under the stirring condition, adjusting the pH value of the solution to 7 by using 0.1mol/L of sodium hydroxide, stirring for 3 hours, after the reaction is finished, centrifugally cleaning, and freeze-drying to obtain the graphene oxide/silicon hydroxide precursor compound.
(2) Preparing graphene-like silicon oxide nanosheets: and (2) putting the graphene oxide/silicon hydroxide precursor compound prepared in the step (1) into a muffle furnace, reacting for 2h at 700 ℃, and cooling to room temperature after the reaction is finished to obtain the graphene-shaped silicon oxide nanosheet.
(3) Preparing a modified graphene-like silicon oxide nanosheet: dispersing the graphene-shaped silicon oxide nanosheets reacted in the step (2) in 50mL of ethanol to prepare 0.005g/mL of ceramic oxide turbid liquid, adding 5g of silane coupling agent, reacting at 80 ℃ for 8h, adding 15mL of water into the mixture after the reaction is finished, stirring for 12h, washing, and freeze-drying to obtain the modified graphene-shaped silicon oxide nanosheets.
(4) Preparing a coating with silicon oxide nano sheets as pigments and fillers: dispersing the modified graphene-shaped silicon oxide nanosheets reacted in the step (3) into n-butanol (the mass ratio of the silicon oxide nanosheets to the n-butanol is 1: 5-20). Then adding epoxy resin, stirring uniformly (the mass ratio of the silicon oxide nano-sheets to the epoxy resin is 1:100), finally adding the mixture into polyamide 650 (the mass ratio of the silicon oxide nano-sheets to the polyamide 650 is 1:20), and mixing uniformly. The viscous mixture was spread evenly on a tinplate by knife coating.
Example 4
The coating taking the magnesium oxide nanosheet as the pigment and filler is prepared according to the following steps:
(1) preparing a graphene oxide/magnesium hydroxide precursor compound: ultrasonically dispersing 30mg of graphene oxide in 20mL of water to prepare 1.5g/mL of graphene oxide turbid liquid, adding 480.21mg of magnesium sulfate under the stirring condition, adjusting the pH value of the solution to 11 by using 0.1mol/L of sodium hydroxide, stirring for 3 hours, after the reaction is finished, centrifugally cleaning, and freeze-drying to obtain the graphene oxide/magnesium hydroxide precursor compound.
(2) Preparing graphene-like magnesium oxide nanosheets: and (2) putting the graphene oxide/magnesium hydroxide precursor compound prepared in the step (1) into a muffle furnace, reacting for 2h at 800 ℃, and cooling to room temperature after the reaction is finished to obtain the graphene-shaped magnesium oxide nanosheet.
(3) Preparing a modified graphene-like magnesium oxide nanosheet: dispersing the graphene-shaped magnesium oxide nanosheets reacted in the step (2) in 50mL of ethanol to prepare 0.005g/mL of ceramic oxide turbid liquid, adding 5g of silane coupling agent, reacting at 80 ℃ for 8h, adding 15mL of water into the mixture after the reaction is finished, stirring for 12h, washing, and freeze-drying to obtain the modified graphene-shaped magnesium oxide nanosheets.
(4) Preparing a coating with magnesium oxide nano-sheets as pigments and fillers: dispersing the modified graphene-shaped magnesium oxide nanosheets reacted in the step (3) into n-butanol (the mass ratio of the magnesium oxide nanosheets to the n-butanol is 1: 5-20). Then adding epoxy resin, stirring uniformly (the mass ratio of the magnesium oxide nanosheet to the epoxy resin is 1:100), finally adding into polyamide 650 (the mass ratio of the magnesium oxide nanosheet to the polyamide 650 is 1:20), and mixing uniformly. The viscous mixture was spread evenly on a tinplate by knife coating.
Example 5
The coating taking calcium oxide nanosheets as pigments and fillers is prepared according to the following steps:
(1) preparing a graphene oxide/calcium hydroxide precursor compound: ultrasonically dispersing 30mg of graphene oxide in 20mL of water to prepare 1.5g/mL of graphene oxide turbid liquid, adding 495.56mg of calcium dichloride under the stirring condition, adjusting the pH value of the solution to 10 by using 0.1mol/L of sodium hydroxide, stirring for 3 hours, centrifugally cleaning after the reaction is finished, and freeze-drying to obtain the graphene oxide/calcium hydroxide precursor compound.
(2) Preparing graphene-like calcium oxide nanosheets: and (2) putting the graphene oxide/calcium hydroxide precursor compound prepared in the step (1) into a muffle furnace, reacting for 2h at 500 ℃, and cooling to room temperature after the reaction is finished to obtain the graphene-shaped calcium oxide nanosheet.
(3) Preparing a modified graphene-like calcium oxide nanosheet: dispersing the graphene-shaped calcium oxide nanosheets reacted in the step (2) in 50mL of ethanol to prepare 0.005g/mL of ceramic oxide turbid liquid, adding 5g of silane coupling agent, reacting at 80 ℃ for 8h, adding 15mL of water into the mixture after the reaction is finished, stirring for 12h, washing, and freeze-drying to obtain the modified graphene-shaped calcium oxide nanosheets.
(4) Preparing a coating with calcium oxide nano-sheets as pigments and fillers: dispersing the modified graphene-shaped calcium oxide nanosheets reacted in the step (3) into n-butanol (the mass ratio of the calcium oxide nanosheets to the n-butanol is 1: 5-20). Then adding epoxy resin, stirring uniformly (the mass ratio of the calcium oxide nano-sheets to the epoxy resin is 1:100), finally adding the mixture into polyamide 650 (the mass ratio of the calcium oxide nano-sheets to the polyamide 650 is 1:20), and mixing uniformly. The viscous mixture was spread evenly on a tinplate by knife coating.
Claims (10)
1. A graphene-shaped ceramic oxide nanosheet pigment and filler is characterized by being a nanosheet material of a ceramic oxide with a graphene lamellar structure.
2. The graphene-like ceramic oxide nanosheet pigment and filler according to claim 1, wherein the ceramic oxide, i.e., the metal oxide, is one of zirconia, alumina, silica, magnesia and calcia.
3. A method of preparing a graphene-like ceramic oxide nanoplate pigment filler according to claim 1 or 2, comprising the steps of:
(1) preparing a graphene oxide/ceramic oxide precursor composite:
ultrasonically dispersing graphene oxide in water to prepare 0.001-10g/ml graphene oxide turbid liquid; adding a ceramic oxide precursor, adjusting the pH value to 7-14, stirring for 0.5-48h, after the reaction is finished, centrifugally cleaning, and freeze-drying to obtain a graphene oxide/ceramic oxide precursor compound;
(2) preparing graphene-like ceramic oxide nanosheets:
putting the graphene oxide/ceramic oxide precursor composite prepared in the step (1) into a muffle furnace, reacting at the temperature of 450-800 ℃ for 1-24h, and cooling to room temperature after the reaction is finished to obtain graphene-shaped ceramic oxide nanosheets;
(3) preparing a modified graphene-shaped ceramic oxide nanosheet:
dispersing the graphene-shaped ceramic oxide nanosheets reacted in the step (2) in ethanol to prepare 0.001-1g/ml of ceramic oxide turbid liquid; adding a silane coupling agent, reacting at 60-90 ℃ for 0.5-48h, adding 1-30mL of water into the mixture after the reaction is finished, stirring for 0.5-48h, washing, and freeze-drying to obtain the modified graphene-shaped ceramic oxide nanosheet.
4. The method according to claim 3, characterized in that the mass ratio of graphene oxide to ceramic oxide precursor is 1:1 to 30.
5. The method according to claim 3, wherein the precursor of the metal oxide is one of zirconium oxychloride octahydrate, aluminum sulfate, silicon tetrachloride, magnesium sulfate and calcium dichloride.
6. The method according to claim 3, characterized in that the mass ratio of the graphene-like ceramic oxide nanosheets to the silane coupling agent is 1: 1-40.
7. A method according to claim 3, characterized in that the silane coupling agent is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane.
8. Use of the graphene-like ceramic oxide nanoplatelet pigment filler of claim 1 or 2 for an anti-corrosive coating.
9. An anticorrosive paint characterized by comprising the graphene-like ceramic oxide nanosheet pigment filler of claim 1 or 2.
10. An anticorrosive coating comprising the graphene-like ceramic oxide nanosheet pigment filler of claim 1 or 2, characterized in that the method of preparing the same comprises the steps of: adding the graphene-shaped ceramic oxide nanosheet pigment filler into an organic solvent (preferably n-butyl alcohol), then adding a film-forming substance and an auxiliary agent, uniformly mixing, and then coating on a metal substrate; wherein the mass ratio of the graphene-shaped ceramic oxide nanosheet pigment filler to the organic solvent is 1: 5-20; the mass ratio of the film forming material to the pigment and filler is 10: 0.01-0.5; the film-forming substance is epoxy resin E44 or epoxy resin E51; the metal substrate is an aluminum sheet, a copper sheet or a tinplate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883646A (en) * | 2017-03-12 | 2017-06-23 | 中国科学院福建物质结构研究所 | Graphene-based coating and its application |
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