CN114621611A - Heating material with graphene sprayed on ceramic surface - Google Patents
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- CN114621611A CN114621611A CN202210342513.5A CN202210342513A CN114621611A CN 114621611 A CN114621611 A CN 114621611A CN 202210342513 A CN202210342513 A CN 202210342513A CN 114621611 A CN114621611 A CN 114621611A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D5/24—Electrically-conducting paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention relates to the technical field of graphene, and discloses a heating material with graphene sprayed on a ceramic surface, which comprises the following steps: s1, preparing materials, preparing graphene: 10-30 parts by mass of a dispersion solvent: 30-800 parts by mass of an electric heating filler: 2-10 parts of auxiliary agent: 1-10 parts by mass of functional filler: 2-8 parts, S2: physically or chemically modifying graphene, S3: and (2) putting the materials into a stirring kettle, stirring for 10min-80min, and carrying out S4: uniformly coating the fully stirred material on the surface of the ceramic, S5: drying the coated ceramic surface for 1-2 h within the temperature range of 100-140 ℃. The electrothermal material sprayed on the surface of the ceramic has electrothermal properties closer to that of intrinsic graphene, and the emulsion and various additives which can perform in-situ esterification, crosslinking and other reactions are added into the graphene dispersion liquid to enhance the binding force between the electrothermal material and the filler, so that the electrothermal material is stable and safe, and the service life is prolonged.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a heating material with graphene sprayed on a ceramic surface.
Background
The atmospheric pollution in China is mainly coal-smoke type pollution, the national coal consumption in recent years, especially the coal consumption for heating in winter is high, the electric heating technology which saves land, is beneficial to environmental protection, is safe and reliable and is simple in charging is implemented, the electrothermal film is a film material which can self-heat after being electrified and is composed of special ink which can conduct electricity and heat, a metal current carrying strip, a base material, a protective layer, a temperature control part, a sensing part and the like, the special conductive ink endows the electrothermal coating with conductivity, the conductive filler mainly comprises metal alloys, carbon materials and the like, and the metal series has excellent conductivity of gold, silver and platinum but high price and is only used in the fields of military affairs and aerospace; copper and aluminum are easy to oxidize, so that the performance is reduced, and the use is limited; the nickel powder is high in density and easy to sink, so that the use is inconvenient, the carbon material has the advantages of light weight, no toxicity, no harm, difficulty in oxidation, low price and the like, and the carbon material is more applied to the field of electric heating coatings, particularly low-temperature electric heating materials, but the existing graphene coating core heating material graphene and various fillers are greatly adsorbed and wrapped by physics, the combination of chemical bond scales is lacked, partial aggregation of effective components is easy to occur in the subsequent storage and use processes, local overheating is easy to cause after devices are manufactured, and potential safety hazards are formed.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the heating material with the graphene sprayed on the ceramic surface, which has the advantages of high safety performance and the like, and solves the problems that the existing graphene coating core heating material, namely the graphene and various fillers are greatly adsorbed and wrapped by physics, the combination of chemical bond scales is lacked, the segregation of effective components is easily generated in the subsequent storage and use processes, and the local overheating and the potential safety hazard are easily caused after a device is manufactured.
(II) technical scheme
In order to achieve the purpose of high safety performance, the invention provides the following technical scheme: a heating material with graphene sprayed on a ceramic surface comprises the following steps:
s1, preparing materials, preparing graphene: 10-30 parts by mass of a dispersion solvent: 30-800 parts by mass of an electric heating filler: 2-10 parts of auxiliary agent: 1-10 parts by mass of a functional filler: 2-8 parts.
S2: and carrying out physical modification or chemical modification on the graphene.
S3: the materials are put into a stirring kettle to be stirred for 10min to 80 min.
S4: and uniformly coating the fully stirred material on the surface of the ceramic.
S5: drying the coated ceramic surface for 1-2 h within the temperature range of 100-140 ℃.
Preferably, the graphene in the S1 is powder or liquid slurry, the graphene nanoplatelets contain one or more of hydroxyl, carboxyl, amino and nitro functional groups, the thickness of the graphene is 0.5-5nm, the transverse dimension is 5-100 μm, the crystal structure is complete, the used dispersion solvent contains one of water, alcohol solvents, ketone solvents and alcohol ether solvents, and the electrothermal filler contains one or more of carbon nanotubes, conductive carbon black and conductive graphite.
Preferably, the various auxiliaries in S1 include one or more of a film-forming aid, a preservative, a defoaming agent, a flame retardant and an adhesion enhancer, the film-forming aid includes one of dodecyl glycol ester, sodium dodecyl benzene sulfonate, propylene glycol butyl ether and propylene glycol methyl ether acetate, the preservative is potassium sorbate, the defoaming agent includes silicone oil, hard fatty amide and aluminum stearate, the flame retardant includes one of antimony trioxide, magnesium hydroxide and aluminum hydroxide, and the adhesion enhancer is one of AP-3000, polydimethylsiloxane, dammar resin and dicyclopentadienyl acrylate monomer.
Preferably, in the physical modification of S2, the surface tension of the graphene nanoplatelets is made to approach the surface tension of the solvent by adding a surfactant to improve the liquid phase dispersibility, wherein the surfactant includes but is not limited to polyoxyethylene ether, cellulose acetate butyrate, polysorbate-80, polyvinyl alcohol, sodium dodecyl sulfate, and sodium dodecyl benzene sulfonate.
Preferably, the S2 chemical modification is performed by introducing a chemical bonding modification method, that is, controllable oxidation is performed on the surface of graphene, carboxyl, hydroxyl and epoxy active groups are optimally introduced, then covalent bonds or ion exchange is introduced by using a chemical reaction between the above groups and other active molecules for chemical modification, and the adopted oxidant includes concentrated sulfuric acid, concentrated nitric acid, hydrogen peroxide and potassium permanganate.
Preferably, the thickness of the coating in S4 is 0.1mm to 0.5 mm.
Compared with the prior art, the invention provides a heating material with graphene sprayed on the surface of ceramic, which has the following beneficial effects:
1. according to the heating material with the graphene sprayed on the ceramic surface, the high-quality graphene stripped by electrochemistry is used as an electric heating material, and compared with other carbon materials, the graphene has lower specific gravity, can effectively reduce the weight of an electric heating material, and can be used in a large area; the graphene has excellent mechanical properties, can be bent and keep good conductivity, has high processability, and meets the requirements of various shapes and applications; the graphene has a high heat conduction coefficient, can quickly dissipate heat, and is uniform and stable in temperature and long in service life. Meanwhile, compared with redox graphene, the electrochemical stripping graphene used in the invention has a more complete crystal structure, the electrothermal property of the electrochemical stripping graphene is closer to that of intrinsic graphene, physical combination (adsorption, wrapping and the like) of graphene and filler in the prior art can be improved into chemical bond combination after in-situ reaction by adding emulsion and various auxiliaries which can perform in-situ esterification, crosslinking and the like into graphene dispersion liquid, the binding force of a heating material and the filler is enhanced, the electrothermal material is stable and safe, and the service life is prolonged.
Detailed Description
The first embodiment is as follows:
a heating material with graphene sprayed on a ceramic surface comprises the following steps:
s1, preparing materials, preparing graphene: 10 parts by mass of graphene, wherein the graphene is powder or liquid slurry, the graphene microchip contains one or more of hydroxyl, carboxyl, amino and nitro functional groups, the thickness of the graphene is 0.5nm, the transverse size of the graphene is 5 mu m, the crystal structure is complete, and the dispersion solution is a solvent: 30 parts by mass of an electrothermal filler, wherein the electrothermal filler comprises one of water, an alcohol solvent, a ketone solvent and an alcohol ether solvent: 2 parts of a mixture containing one or more of carbon nanotubes, conductive carbon black and conductive graphite, and an auxiliary agent: 1 part by mass of the coating comprises one or more of a film-forming assistant, a preservative, a defoaming agent, a flame retardant and an adhesion reinforcing agent, wherein the film-forming assistant comprises one of dodecyl glycol ester, sodium dodecyl benzene sulfonate, propylene glycol butyl ether and propylene glycol methyl ether acetate, the preservative is potassium sorbate, the defoaming agent comprises silicone oil, hard fatty amide and aluminum stearate, the flame retardant comprises one of antimony trioxide, magnesium hydroxide and aluminum hydroxide, the adhesion reinforcing agent is one of polydimethylsiloxane, dammar resin and an acrylic acid dicyclopentadienyl ester monomer, and the functional filler comprises the following components in parts by mass: and 2 parts.
S2: the method comprises the following steps of physically modifying graphene, adding a surfactant to enable the surface tension of graphene nanoplatelets to be close to that of a solvent so as to improve the liquid phase dispersibility, wherein the surfactant comprises but is not limited to polyoxyethylene ether, cellulose acetate butyrate, polysorbate-80, polyvinyl alcohol, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate or chemical modification, introducing a chemical bonding modification method, namely performing controllable oxidation on the surface of the graphene, optimally introducing carboxyl, hydroxyl and epoxy active groups, and then introducing covalent bonds or ion exchange for chemical modification by utilizing the chemical reaction between the groups and other active molecules, wherein the adopted oxidant comprises concentrated sulfuric acid, concentrated nitric acid, hydrogen peroxide and potassium permanganate.
S3: the material was stirred in a stirred tank for 10 min.
S4: and uniformly coating the fully stirred material on the surface of the ceramic, wherein the coating thickness is 0.1 mm.
S5: drying the coated ceramic surface for 1-2 h at the temperature of 100 ℃.
Example two:
a heating material with graphene sprayed on a ceramic surface comprises the following steps:
s1, preparing materials, preparing graphene: 15 parts by mass of graphene, wherein the graphene is powder or liquid slurry, the graphene nanoplatelets contain one or more of hydroxyl, carboxyl, amino and nitro functional groups, the thickness of the graphene is 2nm, the transverse size of the graphene is 40 mu m, the crystal structure is complete, and the dispersion solution is a solvent: 300 parts by mass of water, an alcohol solvent, one of a ketone solvent and an alcohol ether solvent, and an electrothermal filler: 4 parts, including one or a mixture of more of carbon nano tube, conductive carbon black and conductive graphite, and an auxiliary agent: 5 parts by mass of the coating comprise one or more of a film-forming assistant, a preservative, a defoaming agent, a flame retardant and an adhesion reinforcing agent, wherein the film-forming assistant comprises one of dodecyl glycol ester, sodium dodecyl benzene sulfonate, propylene glycol butyl ether and propylene glycol methyl ether acetate, the preservative is potassium sorbate, the defoaming agent comprises silicone oil, hard fatty amide and aluminum stearate, the flame retardant comprises one of antimony trioxide, magnesium hydroxide and aluminum hydroxide, the adhesion reinforcing agent is one of polydimethylsiloxane, dammar resin and an acrylic acid dicyclopentadienyl ester monomer, and the functional filler comprises the following components in parts by mass: 4 parts.
S2: the method comprises the following steps of physically modifying graphene, adding a surfactant to enable the surface tension of graphene nanoplatelets to be close to that of a solvent so as to improve liquid phase dispersibility, wherein the surfactant comprises but is not limited to polyoxyethylene ether, cellulose acetate butyrate, polysorbate-80, polyvinyl alcohol, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate or chemical modification, introducing a chemical bonding modification method, namely controllably oxidizing the surface of the graphene, optimally introducing carboxyl, hydroxyl and epoxy active groups, and then introducing covalent bonds or ion exchange for chemical modification by utilizing chemical reaction between the groups and other active molecules, wherein the adopted oxidant comprises concentrated sulfuric acid, concentrated nitric acid, hydrogen peroxide and potassium permanganate.
S3: the material was stirred in a stirred tank for 40 min.
S4: and uniformly coating the fully stirred material on the surface of the ceramic, wherein the coating thickness is 0.3 mm.
S5: drying the coated ceramic surface for 1-2 h at the temperature of 120 ℃.
Example three:
a heating material with graphene sprayed on a ceramic surface comprises the following steps:
s1, preparing materials, preparing graphene: 15 parts by mass of graphene, wherein the graphene is powder or liquid slurry, the graphene microchip contains one or more of hydroxyl, carboxyl, amino and nitro functional groups, the thickness of the graphene is 3nm, the transverse size of the graphene is 80 mu m, the crystal structure is complete, and the dispersion solution is a solvent: 600 parts by mass of an electrothermal filler, wherein the electrothermal filler comprises one of water, an alcohol solvent, a ketone solvent and an alcohol ether solvent: 7 parts, including one or a mixture of more of carbon nano tube, conductive carbon black and conductive graphite, and an auxiliary agent: 8 parts by mass of the coating agent comprise one or more of a film forming aid, a preservative, a defoaming agent, a flame retardant and an adhesion force enhancer, wherein the film forming aid comprises one of dodecyl glycol ester, sodium dodecyl benzene sulfonate, propylene glycol butyl ether and propylene glycol methyl ether acetate, the preservative is potassium sorbate, the defoaming agent comprises silicone oil, hard fatty amide and aluminum stearate, the flame retardant comprises one of antimony trioxide, magnesium hydroxide and aluminum hydroxide, the adhesion force enhancer is one of polydimethylsiloxane, dammar resin and acrylate dicyclopentadienyl ester monomers, and the functional filler comprises the following components in parts by mass: 7 parts.
S2: the method comprises the following steps of physically modifying graphene, adding a surfactant to enable the surface tension of graphene nanoplatelets to be close to that of a solvent so as to improve liquid phase dispersibility, wherein the surfactant comprises but is not limited to polyoxyethylene ether, cellulose acetate butyrate, polysorbate-80, polyvinyl alcohol, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate or chemical modification, introducing a chemical bonding modification method, namely controllably oxidizing the surface of the graphene, optimally introducing carboxyl, hydroxyl and epoxy active groups, and then introducing covalent bonds or ion exchange for chemical modification by utilizing chemical reaction between the groups and other active molecules, wherein the adopted oxidant comprises concentrated sulfuric acid, concentrated nitric acid, hydrogen peroxide and potassium permanganate.
S3: the material was stirred in a stirred tank for 60 min.
S4: and uniformly coating the fully stirred material on the surface of the ceramic, wherein the coating thickness is 0.4 mm.
S5: drying the coated ceramic surface for 1-2 h at the temperature of 130 ℃.
Example four:
a heating material with graphene sprayed on a ceramic surface comprises the following steps:
s1, preparing materials, preparing graphene: 30 parts by mass of graphene, wherein the graphene is powder or liquid slurry, the graphene nanoplatelets contain one or more of hydroxyl, carboxyl, amino and nitro functional groups, the thickness of the graphene is 5nm, the transverse size is 100 mu m, the crystal structure is complete, and the dispersion solution solvent is as follows: 800 parts by mass, comprising one of water, alcohol solvent, ketone solvent and alcohol ether solvent, and electrothermal filler: 10 parts, including one or a mixture of more of carbon nano tube, conductive carbon black and conductive graphite, and an auxiliary agent: 10 parts by mass of the coating agent comprise one or more of a film forming aid, a preservative, a defoaming agent, a flame retardant and an adhesion force enhancer, wherein the film forming aid comprises one of dodecyl glycol ester, sodium dodecyl benzene sulfonate, propylene glycol butyl ether and propylene glycol methyl ether acetate, the preservative is potassium sorbate, the defoaming agent comprises silicone oil, hard fatty amide and aluminum stearate, the flame retardant comprises one of antimony trioxide, magnesium hydroxide and aluminum hydroxide, the adhesion force enhancer is one of polydimethylsiloxane, dammar resin and acrylate dicyclopentadienyl ester monomers, and the functional filler comprises the following components in parts by mass: 8 parts.
S2: the method comprises the following steps of physically modifying graphene, adding a surfactant to enable the surface tension of graphene nanoplatelets to be close to that of a solvent so as to improve liquid phase dispersibility, wherein the surfactant comprises but is not limited to polyoxyethylene ether, cellulose acetate butyrate, polysorbate-80, polyvinyl alcohol, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate or chemical modification, introducing a chemical bonding modification method, namely controllably oxidizing the surface of the graphene, optimally introducing carboxyl, hydroxyl and epoxy active groups, and then introducing covalent bonds or ion exchange for chemical modification by utilizing chemical reaction between the groups and other active molecules, wherein the adopted oxidant comprises concentrated sulfuric acid, concentrated nitric acid, hydrogen peroxide and potassium permanganate.
S3: the material was stirred in a stirred tank for 80 min.
S4: and uniformly coating the fully stirred material on the surface of the ceramic, wherein the coating thickness is 0.5 mm.
S5: drying the coated ceramic surface for 2h at the temperature of 140 ℃.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. A heating material with graphene sprayed on a ceramic surface comprises the following steps:
s1, preparing materials, preparing graphene: 10-30 parts by mass of a dispersion solvent: 30-800 parts by mass of an electric heating filler: 2-10 parts of auxiliary agent: 1-10 parts by mass of functional filler: 2-8 parts;
s2: carrying out physical modification or chemical modification on graphene;
s3: placing the materials in a stirring kettle, and stirring for 10-80 min;
s4: uniformly coating the fully stirred material on the surface of the ceramic;
s5: drying the coated ceramic surface for 1-2 h within the temperature range of 100-140 ℃.
2. The heat-generating material with graphene sprayed on a ceramic surface according to claim 1, characterized in that: the graphene in the S1 is powder or liquid slurry, the graphene nanoplatelets contain one or more of hydroxyl, carboxyl, amino and nitro functional groups, the thickness of the graphene is 0.5-5nm, the transverse dimension is 5-100 mu m, the crystal structure is complete, the used dispersion liquid solvent contains one of water, alcohol solvents, ketone solvents and alcohol ether solvents, and the electrothermal filler contains one or more of carbon nanotubes, conductive carbon black and conductive graphite.
3. The heat-generating material with graphene sprayed on a ceramic surface according to claim 1, characterized in that: the anti-foaming agent in the S1 comprises one or more of a film-forming aid, a preservative, a defoaming agent, a flame retardant and an adhesion force enhancer, wherein the film-forming aid comprises one of glycol dodecyl ester, sodium dodecyl benzene sulfonate, propylene glycol butyl ether and propylene glycol monomethyl ether acetate, the preservative is potassium sorbate, the defoaming agent comprises silicone oil, hard fatty amide and aluminum stearate, the flame retardant comprises one of antimony trioxide, magnesium hydroxide and aluminum hydroxide, and the adhesion force enhancer is one of AP-3000, polydimethylsiloxane, dammar resin and dicyclopentadienyl acrylate monomer.
4. The heat-generating material with graphene sprayed on a ceramic surface according to claim 1, characterized in that: in the step S2, physical modification is performed, and a surfactant is added to enable the surface tension of the graphene nanoplatelets to be close to that of a solvent so as to improve the liquid phase dispersibility, wherein the surfactant includes but is not limited to polyoxyethylene ether, cellulose acetate butyrate, polysorbate-80, polyvinyl alcohol, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
5. The heat-generating material with graphene sprayed on a ceramic surface according to claim 1, characterized in that: and S2 chemical modification, namely, carrying out controllable oxidation on the surface of graphene by introducing a chemical bonding modification method, optimally introducing carboxyl, hydroxyl and epoxy active groups, and then introducing covalent bonds or ion exchange for chemical modification by utilizing the chemical reaction between the groups and other active molecules, wherein the adopted oxidant comprises concentrated sulfuric acid, concentrated nitric acid, hydrogen peroxide and potassium permanganate.
6. The heat-generating material with graphene sprayed on a ceramic surface according to claim 1, characterized in that: the thickness of the coating in the S4 is 0.1mm-0.5 mm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210342513.5A CN114621611A (en) | 2022-04-02 | 2022-04-02 | Heating material with graphene sprayed on ceramic surface |
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| CN202210342513.5A CN114621611A (en) | 2022-04-02 | 2022-04-02 | Heating material with graphene sprayed on ceramic surface |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906832A (en) * | 2016-06-29 | 2016-08-31 | 德阳烯碳科技有限公司 | Preparation method of graphene-containing water-based electrothermal film |
| CN107384026A (en) * | 2017-08-22 | 2017-11-24 | 华惠福科技股份有限公司 | A kind of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink and preparation method |
| CN107682943A (en) * | 2017-09-20 | 2018-02-09 | 中国科学院山西煤炭化学研究所 | A kind of multifunctional graphite vinyl electric heating slurry and its manufactured Multifunctional electrothermic film and preparation method and application |
| CN109587842A (en) * | 2018-11-08 | 2019-04-05 | 中国科学院山西煤炭化学研究所 | A kind of graphene-based self limiting temperature electric heating slurry and preparation method thereof and the application in electric heating floor system |
-
2022
- 2022-04-02 CN CN202210342513.5A patent/CN114621611A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906832A (en) * | 2016-06-29 | 2016-08-31 | 德阳烯碳科技有限公司 | Preparation method of graphene-containing water-based electrothermal film |
| CN107384026A (en) * | 2017-08-22 | 2017-11-24 | 华惠福科技股份有限公司 | A kind of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink and preparation method |
| CN107682943A (en) * | 2017-09-20 | 2018-02-09 | 中国科学院山西煤炭化学研究所 | A kind of multifunctional graphite vinyl electric heating slurry and its manufactured Multifunctional electrothermic film and preparation method and application |
| CN109587842A (en) * | 2018-11-08 | 2019-04-05 | 中国科学院山西煤炭化学研究所 | A kind of graphene-based self limiting temperature electric heating slurry and preparation method thereof and the application in electric heating floor system |
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