CN115029022B - High-temperature electric heating slurry, electric infrared heating film and preparation method - Google Patents
High-temperature electric heating slurry, electric infrared heating film and preparation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0209—Multistage baking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- 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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09D161/14—Modified phenol-aldehyde condensates
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
Abstract
The embodiment of the application provides high-temperature electric heating slurry, an electric infrared heating film and a preparation method, and relates to the field of high-temperature electric heating materials. The high-temperature electric heating slurry adopts low-defect graphene with high temperature resistance, realizes the compounding of nano ceramic powder and graphene with large specific surface by a mechanical method, forms a crosslinked structure by utilizing the dehydration polycondensation reaction between phosphoric acid glue and nano ceramic powder under an acidic condition, and improves the structural stability and the working stability of the material at high temperature by means of inhibiting the dimensional change of the graphene caused by electrifying and heating together with boron nitride nano sheets. The boron nitride electric infrared heating film is mainly obtained by coating and curing the high-temperature electric heating slurry. The electric heating material can work in air at the high temperature of more than 400 ℃ for more than 3000 hours, and meets the requirements of the high-temperature electric heating material.
Description
Technical Field
The application relates to the field of high-temperature electric heating materials, in particular to high-temperature electric heating slurry, an electric infrared heating film and a preparation method.
Background
Because the carbon heating material, especially the heating material represented by the novel carbon materials such as graphene, carbon fiber, carbon crystal and the like, has high electrothermal conversion rate, and the infrared wavelength radiated during working can be widely used in the application fields such as food heating, human body heating and the like, the carbon heating material has gained wide attention in the market and the heating product industry. Although various carbon heating coatings developed based on conductive ink are easy to process into electric heating products with small volume, high integration level and rapid temperature rise, such as heating films, the carbon heating products with the working temperature of more than 300 ℃ and corresponding material technologies are still in a development stage at present.
The existing carbon heating material is difficult to be used as an electric heating material main body to work at high temperature for a long time, and the following four reasons are mainly included: 1) Most of the film forming agents (binders) in carbon heating coatings are organic resin materials, and mechanical property cliff-like reduction can occur at high temperature of more than 400 ℃ and react with oxygen in the air. 2) The conventional inorganic curing agent has volume change in the process of complete curing and temperature change of hundreds of degrees celsius, so that the coating structure and a conductive loop formed by the carbon material are damaged, and the electric heating material is broken. 3) Most carbon materials are easy to generate irreversible oxidation-reduction reaction with air and other components in the paint under the high-temperature environment of more than 400 ℃, so that the power is unstable and the application is difficult. 4) The volume change and thermal movement of most carbon materials in the temperature change process of hundreds of DEG C can cause the change of a microcosmic conductive system, thereby causing the unstable conductive performance of the coating.
Disclosure of Invention
The embodiment of the application aims to provide high-temperature electric heating slurry, an electric infrared heating film and a preparation method, wherein an electric heating material can work in air at a high temperature of more than 400 ℃ for more than 3000 hours, and the requirement of the high-temperature electric heating material is met.
In a first aspect, embodiments of the present application provide a high temperature electrically heated slurry comprising a solvent and components dispersed in the solvent, the components comprising, in parts by weight: 5-15 parts of low-defect graphene, 4-18 parts of boron nitride, 3-13 parts of high-temperature resistant curing agent and 4-20 parts of ceramic oxide;
in the Raman spectrum diagram of the low-defect graphene, the ratio of the D peak intensity to the G peak intensity is not more than 1/10, and the carbon-oxygen mole ratio in the low-defect graphene is not less than 20:1, a step of;
the high temperature resistant curing agent comprises phosphoric acid and aluminum dihydrogen phosphate;
the ceramic oxide is at least one of aluminum oxide and silicon oxide.
In the technical scheme, the active components in the high-temperature electric heating slurry are composed of low-defect graphene, boron nitride, a high-temperature-resistant curing agent and ceramic oxide, wherein the high-temperature-resistant curing agent at least comprises phosphoric acid glue (phosphoric acid and aluminum dihydrogen phosphate), and the high-temperature-resistant curing agent and the ceramic oxide act together to meet the high-temperature electric heating requirement. The low-defect graphene has a special electronic structure, has extremely high electron affinity, and has higher oxidation resistance compared with a carbon material with a general graphite-like structure; in addition, the single-layer/few-layer graphene has extremely high lamellar geometric structure characteristics under the sheet diameter of 10 microns, and can realize a surface-surface overlapped conductive network link structure.
In addition, as the graphene generates heat movement in the process of electrifying and heating, the three-dimensional conductive network is damaged, ceramic powder is adopted for compounding, and then phosphate-oxide ceramic curing system is formed by the reaction of phosphate glue and the ceramic powder, so that unstable power and coating damage are avoided. According to the embodiment of the application, the boron nitride is adopted as the structural filler, the heat conduction is high, the thermal expansion coefficient is low, the structure is stable, meanwhile, the boron nitride is also a compact two-dimensional material, the inner and outer heat exchange efficiency of the film layer is improved, and the film layer is prevented from being damaged by thermal stress formed by large inner and outer temperature difference of the film layer. The structural stability and the working stability of the material at high temperature are finally ensured by the boron nitride.
In one possible implementation, the D50 particle size of the low defect graphene is 10-15 μm, and the mass loss rate of calcining in air at 550 ℃ for 12 hours is less than 2wt%;
and/or the D50 particle size of the boron nitride is 10-15 μm.
And/or the D50 particle size of the ceramic oxide is 10-60nm.
In one possible implementation, the mass ratio of ceramic oxide to low defect graphene is 1:2-14:3;
and/or the ceramic oxide is silicon oxide and aluminum oxide, the D50 granularity of the silicon oxide is 10-30nm, and the D50 granularity of the aluminum oxide is 20-40nm.
In one possible implementation, the high temperature resistant curing agent further comprises at least one of a silicate, a polyamideimide, a modified phenolic resin, and a modified polyimide.
In one possible implementation, it further comprises a dispersant dissolved in the solvent, the dispersant comprising at least one of hydroxyalkyl ethers, hydroxy isomeric alcohols, ethylene oxide, polyethylene glycol, dibasic acid esters, hydroxypropyl methylcellulose, polyvinylpyrrolidone;
alternatively, the dispersant is a hydroxyalkyl ether or polyvinylpyrrolidone.
In the above technical scheme, due to the electronic characteristics of the exposed surface of the low-defect graphene, the dispersion effect of the common ionic dispersing agent on the graphene is poor, and the adoption of the high-molecular dispersing agent as the main dispersing agent can cause coating gas expansion easily when the high-temperature unstable large-scale dispersing agent is adopted, so that the conductive loop formed by the graphene is damaged. The dispersing agent selected by the application is hydroxyalkyl ether with low saturated vapor pressure and a small amount of polymer surfactant (such as polyvinylpyrrolidone), so that the dispersion of graphene can be effectively realized, and meanwhile, most dispersing agent is ensured to be removed simultaneously with moisture in the low-temperature drying process, and the coating is prevented from being damaged due to gas expansion in the curing process and the high-temperature working process.
In one possible implementation, the solvent includes at least one of deionized water, N-methylpyrrolidone.
In a second aspect, an embodiment of the present application provides a method for preparing the high-temperature electric heating slurry provided in the first aspect, including the following steps:
blending and sanding low-defect graphene, boron nitride, ceramic oxide and a solvent;
and adding a high-temperature-resistant curing agent, and mixing to obtain the high-temperature-resistant epoxy resin.
In the technical scheme, firstly, low-defect graphene, boron nitride, ceramic oxide and a solvent are blended and sanded to obtain proper particle size of the graphene, a graphene sheet is opened, boron nitride powder is inserted and compounded with the ceramic oxide powder to form a bonding anchor point, and the powder of each component is dispersed; and adding a high-temperature-resistant curing agent to form slurry for curing reaction.
In one possible implementation, it includes the steps of:
uniformly mixing a dispersing agent and a solvent to obtain a composite base solution, adding low-defect graphene, boron nitride and ceramic oxide into the composite base solution, continuously stirring until the low-defect graphene, the boron nitride and the ceramic oxide are uniformly dispersed in the composite base solution, and sanding at a linear speed of 10-20m/s by taking zirconium balls with the diameter of 0.1-0.5mm as grinding media to obtain a dispersion liquid;
adding high temperature resistant curing agent into the dispersion liquid, and stirring at the speed of 200-500rpm at the temperature of 35-50 ℃ for 1-3h.
In a third aspect, embodiments of the present application provide an infrared electrothermal film, which is mainly obtained by coating and curing the high-temperature electric heating slurry provided in the first aspect.
In a fourth aspect, embodiments of the present application provide a method for preparing an electric infrared heating film, including the steps of:
coating the high-temperature electric heating slurry provided in the first aspect on a substrate, and drying and shaping at 40-70 ℃;
heating to 150-300 ℃ and preserving heat for 0.3-1h, then heating to 400-600 ℃ and preserving heat for 0.5-2 h, and sintering.
In the technical scheme, after coating, drying and shaping are carried out at low temperature, the solvent and most of the auxiliary agent are discharged, a small amount of auxiliary agent is discharged after high-temperature sintering, the phosphoric acid glue is solidified, and the stress of the coating is released.
Detailed Description
The applicant finds that most curing agents (binders) used in the existing vast majority of sizing agents and paint vehicles are commonly used organic resin curing agents, and the following problems exist in the organic resin materials: the temperature resistance in the air is insufficient, and the reaction with the air is easy; the glass transition temperature is low, and the mechanical property is reduced by cliff jump at high temperature; and the thermal expansion and the structural stability at high temperature are insufficient.
In addition, the electric heating material formed by several commonly used inorganic binders cannot stably work in an air environment of 400 ℃ or more.
When the glass powder is used as a binder, high-temperature calcination is needed, the powder-softening-solidification process is carried out, the internal structure of the coating is greatly changed in the two phase changes, the strain is obvious, and the brittle fracture of the film layer is easy to occur due to the fact that the carbon filler has high volume ratio and the thermal expansion is obvious.
The dissolution of silicate requires a strong alkali environment, which is not beneficial to the dispersion of graphene; water glass has similar problems to silicate.
The bonding strength of pure-phase phosphate and the electrothermal filler is insufficient, and pulverization is easy to occur after sintering to form a film.
Through a great deal of research, the application finds that the phosphate gel (phosphoric acid and aluminum hydrogen phosphate) can react with graphene and specific ceramic oxide (aluminum oxide and/or silicon oxide) to produce a high-temperature-resistant electric heating material by adopting the phosphate gel (phosphoric acid and aluminum hydrogen phosphate) as a curing agent, and phosphoric acid stabilizes an aluminum hydrogen phosphate component on one hand and provides an acidic environment to enable the phosphate to react with the aluminum oxide and/or silicon oxide to form a bond on the other hand. In the forming process of the slurry, the concentration of the phosphate gum rises along with the evaporation of the solvent, and the phosphate gum can continuously react with the specific ceramic oxide to improve the film forming property of the slurry.
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The high-temperature electric heating slurry, the electric infrared heating film and the preparation method of the embodiment of the application are specifically described below.
The embodiment of the application provides high-temperature electric heating slurry, which comprises a solvent and components dispersed in the solvent, wherein the components comprise the following components in parts by weight: 5-15 parts of low-defect graphene, 4-18 parts of boron nitride, 3-13 parts of high-temperature resistant curing agent/binder/film forming agent, 4-20 parts of ceramic oxide and 8-12 parts of dispersing agent dissolved in a solvent.
Wherein the main solvent is at least one of deionized water and N-methyl pyrrolidone, and the mass ratio of the solvent is generally 60% -75%.
In the Raman spectrum diagram of the low-defect graphene, the ratio of the D peak intensity to the G peak intensity is not more than 1/10, and the carbon-oxygen mole ratio in the low-defect graphene is not less than 20:1, the mass loss rate of calcination in air at 550 ℃ for 12 hours is less than 2wt%. The low-defect graphene in the high-temperature electric heating slurry is powder, and the D50 particle size of the low-defect graphene is 10-15 mu m.
The boron nitride in the high-temperature electric heating slurry is powder, and the D50 granularity of the boron nitride is 10-15 mu m. In addition to boron nitride as a structural filler, other fillers may be added, optionally including at least one of titanium oxide, zirconium oxide, silicon carbide, mica.
The high-temperature-resistant curing agent comprises phosphoric acid and aluminum dihydrogen phosphate, and can also comprise at least one of silicate, polyamide-imide, modified phenolic resin and modified polyimide according to the actual application requirements.
The ceramic oxide in the embodiment of the application refers to a ceramic oxide capable of reacting with phosphoric acid glue, and specifically, the ceramic oxide is at least one of alumina and silica; the ceramic oxide in the high-temperature electric heating slurry is powder, and the D50 granularity of the ceramic oxide is 10-60nm. As one embodiment, the mass ratio of ceramic oxide to low defect graphene is 1:2-14:3; the ceramic oxide is nano-scale silicon dioxide powder and nano-scale alumina powder, and the mass ratio of the nano-scale silicon dioxide powder to the nano-scale alumina powder can be 1:2-5, the D50 granularity of the silicon dioxide is 10-30nm, and the D50 granularity of the aluminum oxide is 20-40nm.
The dispersing agent comprises a slurry dispersing agent and a film dispersing agent; the slurry dispersing agent is selected from one or any combination of hydroxyalkyl ethers, hydroxyl isomerism alcohol, ethylene oxide, polyethylene glycol, dibasic acid ester, hydroxypropyl methyl cellulose and polyvinylpyrrolidone. As one embodiment, the dispersant comprises hydroxyalkyl ethers and polyvinylpyrrolidone with a mass ratio of 3-6:1.
the embodiment of the application also provides a preparation method of the high-temperature electric heating slurry, which comprises the following steps:
1. blending and sanding low-defect graphene, boron nitride, ceramic oxide, a dispersing agent and a solvent to obtain a dispersing liquid, wherein the specific process is as follows:
uniformly mixing a dispersing agent and a solvent to obtain a composite base solution, adding low-defect graphene, boron nitride and ceramic oxide into the composite base solution, continuously stirring until the low-defect graphene, boron nitride and ceramic oxide are uniformly dispersed in the composite base solution, and sanding at a linear speed of 10-20m/s by taking zirconium balls with the diameter of 0.1-0.5mm as grinding media to obtain a dispersion liquid.
2. Adding high temperature resistant curing agent into the dispersion, mixing uniformly, and stirring at a speed of 200-500rpm for 1-3h at 35-50 ℃ to obtain high temperature electric heating slurry.
The embodiment of the application also provides an electric infrared heating film which is mainly obtained by coating and curing the high-temperature electric heating slurry, wherein the thickness of the electric infrared heating film is generally 10-30 mu m.
The embodiment of the application also provides a preparation method of the electric infrared heating film, which comprises the following steps:
(1) The high-temperature electric heating slurry is coated on a base material, which can be a quartz plate, and is dried and shaped at 40-70 ℃.
(2) Heating to 150-300 deg.c, maintaining for 0.3-1 hr, heating to 400-600 deg.c, maintaining for 0.5-2 hr, and sintering.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The embodiment provides high-temperature electric heating slurry which mainly comprises a solvent and the following components in parts by weight: 8 parts of low-defect graphene, 12 parts of boron nitride microchip, 12 parts of high-temperature resistant curing agent and 15 parts of ceramic oxide. Wherein the D50 granularity of the low-defect graphene is 12 mu m, the Raman spectrum of the low-defect graphene has 2D peaks, and the distance between the 2D peaks and the G peaks is reduced by 5cm compared with that between the 2D peaks and the G peaks of the natural crystalline flake graphite -1 The ratio of the D peak intensity to the G peak intensity is 1/20, and the carbon-oxygen molar ratio of the low-defect graphene is 30:1; the D50 granularity of the boron nitride is 12 mu m; the high-temperature resistant curing agent is phosphoric acid glue (the solid content is 40wt percent, the volatilizable part is not counted into a main solvent, and the description is omitted below); the ceramic oxide is nano silicon dioxide with the granularity of D50 of 20nm and nano aluminum oxide with the granularity of D50 of 30nm, and the ratio of the two is 1:2.
the preparation method of the high-temperature electric heating slurry comprises the following steps:
(1) Crushing the low-defect graphene raw material by airflow to obtain low-defect graphene powder;
(2) Uniformly mixing a dispersing agent (the dispersing agent is isomeric alcohol polyoxyethylene ether and polyvinylpyrrolidone PVP K30, the mass ratio of the isomeric alcohol polyoxyethylene ether to the polyvinylpyrrolidone is 5:2) and a main solvent (the main solvent is deionized water), completely dissolving the dispersing agent in the main solvent to obtain a composite base solution, adding low-defect graphene powder, boron nitride and ceramic oxide into the composite base solution, continuously stirring until the low-defect graphene powder, the boron nitride and the ceramic oxide are uniformly dispersed in the composite base solution, and sanding at a linear speed of 15m/s by taking zirconium balls of 0.3mm as grinding media at 20 ℃ to obtain a low-defect graphene dispersion; then, a high temperature resistant curing agent and a thickener (polyethylene oxide MW800 ten thousand) were added to the low defect graphene dispersion, and then stirred at a speed of 300rpm at 40℃for 2 hours, to obtain a high temperature electric heating slurry.
The high temperature electric heating slurry has a solid content of 15.96wt% and a viscosity of 1600 Pa.s, wherein: 3.16% of dispersant (0.9% of polyvinylpyrrolidone); the mass ratio of the main solvent is 75.36%; the mass ratio of the low-defect graphene powder is 3.01%; the mass ratio of the boron nitride is 4.52%; the mass ratio of the ceramic oxide is 5.65%; the mass ratio of the high-temperature-resistant curing agent is 4.52 percent, and the mass ratio of the thickening agent is 0.06 percent.
The embodiment also provides an electric infrared heating film, the thickness of which is 10 μm, and the preparation method comprises the following steps:
(1) The high-temperature electric heating slurry of the embodiment is coated on a quartz plate by a flat blade coater to form a coating, and is dried and shaped at 60 ℃.
(2) And (3) placing the shaped flat plate into a muffle furnace, heating to 200 ℃ at 5 ℃/min, preserving heat for 30 min, heating to 500 ℃ at 2 ℃/min, preserving heat for 1 hour, and sintering to obtain the electric infrared heating film.
Example 2
This example provides a high temperature electric heating slurry, which is different from example 1 in the preparation method thereof:
(2) Uniformly mixing a dispersing agent (dibasic acid ester and polyethylene glycol, MW=200, liquid, the mass ratio of the dibasic acid ester to the polyethylene glycol is 9:1) and a main solvent (N-methylpyrrolidone) to obtain a composite base solution, then adding low-defect graphene powder, boron nitride and ceramic oxide into the composite base solution, continuously stirring until the low-defect graphene powder, the boron nitride and the ceramic oxide (aluminum oxide) are uniformly dispersed in the composite base solution, and then grinding at a linear speed of 15m/s by taking zirconium balls of 0.3mm as grinding media at 20 ℃ to obtain a low-defect graphene dispersion; then adding a high-temperature-resistant curing agent (modified phenolic resin) and a dispersing agent (hydroxymethyl cellulose) into acetone, adding the dispersing liquid after complete dissolution, then adding ethanol and the high-temperature-resistant curing agent (phosphate gum, solid content of 40 wt%) after stirring at a speed of 300rpm for 30 minutes at 40 ℃ and continuing stirring for 2 hours, wherein the mass ratio of the acetone to the ethanol to the hydroxymethyl cellulose is 9:1:0.05 to obtain high-temperature electric heating slurry.
The high temperature electrically heated slurry had a solids content of 14.58wt% and a viscosity of 1500 Pa.s, wherein: the mass ratio of the dispersing agent is 6.91 percent (wherein, the hydroxymethyl cellulose accounts for 0.07 percent), the mass ratio of the main solvent accounts for 61.6 percent, the mass ratio of the low-defect graphene powder is 3.42 percent, the mass ratio of the boron nitride accounts for 2.74 percent, the mass ratio of the ceramic oxide accounts for 2.74 percent, and the high-temperature resistant curing agent accounts for 8.9 percent of the mass of the film-making slurry (the mass ratio of the modified phenolic resin to the phosphoric acid adhesive is 5:8).
The present embodiment also provides an infrared electrothermal film, which is different from embodiment 1 in the preparation method thereof: the high-temperature electric heating paste of this example was applied to a substrate with a flat blade coater to finally obtain an electric infrared heating film having a thickness of 15. Mu.m.
Examples 3 to 4
Each example provides a high temperature electrically heated slurry and corresponding electrically infrared heating film, respectively, prepared in substantially the same manner as in example 1.
The parts by weight of low-defect graphene and ceramic oxide in the electric infrared heating film in examples 1 to 4, the particle size of the low-defect graphene, the type and particle size of the ceramic oxide and the thickness of the electric infrared heating film are shown in Table 1; the compositions of the high temperature electric heating pastes in examples 1 to 4 are shown in Table 2; the solids content and viscosity of the IR heat generating films in examples 1-4 and the types of flat substrate used are shown in Table 3.
The low defect graphene raw materials in examples 1-4 were purchased from zheng state new materials technology limited and were prepared by physical swelling method; the modified phenolic resin is a commercially available modified phenolic resin commodity with the temperature resistance of up to 600 ℃; the phosphate gum is a mixture of aluminum dihydrogen phosphate, aluminum phosphate and concentrated phosphoric acid (the solute accounts for about 40 percent); the preparation of the electric infrared heating film is 80 x 100mm rectangular coating prepared by controlling the coating cutter head and the coating stroke. The preparation methods of tables 1 to 3 are the same as those of example 1, and are not repeated.
TABLE 1 slurry compositions of examples 1-4
TABLE 2 specific compositions of the slurries of examples 3-4
TABLE 3 slurries of examples 1-4, substrates used and product parameters
Comparative examples 1 to 14
Comparative example 1 was a commercial carbon fiber heating wire, and the temperature was raised to 400 ℃ by breaking the quartz/glass tube body of a general commercial carbon fiber heating tube, leaving only the carbon fiber heating body and electrode structure directly energized.
Comparative example 2 is a commercial microcrystalline hotplate rated for operating temperatures <260 ° (eilda).
The electric infrared heating films of comparative examples 3 to 7 were self-made by various carbon materials commercially available, and were different from example 1 only in the electric infrared heating films on quartz plates: preparation of the electroinfrared heating film on the quartz plate of comparative examples 3 to 7 referring to the preparation method of the electroinfrared heating film of example 1, the difference is that comparative examples 3 to 7 are only to remove boron nitride micro-plates or to replace low defect graphene with other carbon materials, see table 4 in detail, and are not described in the specification of example 1.
Preparation of the electric infrared heating film on the quartz plate of comparative examples 8 to 9 referring to the preparation method of the electric infrared heating film of example 1, the difference is that the ceramic oxide powder compounded with the low-defect graphene is replaced with the filler powder titanium dioxide and zirconium oxide, respectively.
Preparation of the electric infrared heating film on the quartz plate of comparative examples 10 to 12 referring to the preparation method of the electric infrared heating film of example 1, the difference is that the high temperature resistant curing agent used was replaced with water glass, aluminum phosphate and polyimide wet powder (40 wt%) respectively.
Preparation of the electric infrared heating films on the quartz plates of comparative examples 13 to 14 referring to the preparation method of the electric infrared heating film of example 1, the difference is that the dispersing agents used are polyvinylpyrrolidone and sodium polyacrylate.
TABLE 4 composition of the corresponding slurries for the IR-sensitive films of comparative examples 3-7 and the conditions after sintering of the coating
The viscosity of the paint formed in comparative examples 8-9 is less than 300Pa s, and after the coating is sintered, the surface layer of the film layer is chalked and dropped. Because sintering has a large damage to the integrity of the film, no power-on test is performed for safety.
Comparative examples 10-12 showed powder loss on the surface of the film after sintering of the coating, and the film integrity was substantially intact, and after judgment, subsequent test experiments were performed.
Comparative examples 13-14 showed pinholes in the film after sintering of the coating, and the film remained generally intact, and after judgment, subsequent experiments were performed.
Temperature resistance test in air environment
Since the coatings of comparative examples 3 to 5 were significantly increased in resistance during sintering in air, the color thereof was changed from black to gray, and it was determined that the subsequent endurance test at 400 ℃ was not performed, and thus the temperature resistance test was not performed any more, and the temperature resistance test subjects of the present test were the samples of examples 1 to 4 and comparative examples 1, 2, 6, 7, 10 to 14.
Wherein, the comparative example 1 and the comparative example 2 are commercial products, and can be directly subjected to temperature rise and endurance test by connecting a constant voltage power supply, and the self-made electric infrared heating films of other examples and the comparative example are coated with silver paste along the short side in parallel and then are provided with molybdenum sheet electrodes with the width of 15mm and the thickness of 2mm, and are connected with the power supply for testing.
Experimental example 1
The test specimens were energized with an alternating current of 50Hz, the voltage was increased at a rate of 1V/min until the specimens heated to 400℃for 30 minutes and the voltage and power were recorded, and the results are shown in Table 5.
Table 5 experimental results of examples and comparative examples in experimental example 1
As is clear from Table 5, the general commercial carbon fiber heating body material of comparative example 1 was insufficient in stability when operated at 400℃in air, and endurance test was not performed for safety and necessity. The sealing material of the microcrystalline heating plate of comparative example 2 cannot meet the long-time heating at 400 ℃. Compared with redox graphene, the thermal stability of the repair graphene oxide adopted in the comparative example 6 in the air is greatly improved due to fewer defects; likewise, examples 1-4 employ low defect graphene as referred to in this application. The stability of all examples is good, confirming the point of view of the importance of the temperature resistant carbon material among the 4 key factors presented in this application. Meanwhile, the addition of the boron nitride material microchip can be found to have a remarkable effect on improving the overall working stability of the material by stabilizing the material microstructure in the heating process through the comparative example 7, and the view of the structural stability under thermal expansion among 4 key factors provided in the application is verified again.
Experimental example 2
The sample with better stability in the experimental example 1 is subjected to an accelerated aging endurance test of over-temperature and over-power according to the conversion mode described in the 22 nd item in GB/T7287-2008, the equivalent life of the sample is recorded by taking the power attenuation less than or equal to 5% as a judgment life index and taking 12 hours as an interval, and the experimental result is shown in Table 6.
Table 6 experimental results of examples and comparative examples in experimental example 2
In experimental example 2, the coating of comparative example 6 was found to be significantly burned out at some point of the heat-generating region of the coating made of reduced graphene oxide after the first 12 hours.
The coating in comparative example 7 was found to be significantly warped after breakage from a certain center point after the first 12 hours; the surface pulverization phenomenon occurring on the surface after the sintering process is finished and the phenomenon of small power rise in experimental example 1 are combined, so that the phenomenon can be deduced that the material is overheated due to the fact that the volume expansion rate of graphene is inconsistent with the thermal expansion rate of the binder solidified material and has large difference, and the internal structure of the electrothermal material is unstable at high temperature for a long time.
In all of examples 1 to 4, the equivalent lifetime of 4000 hours or more was exhibited, and the practical value as a heat generating body material was found.
As can be seen from comparison of example 4 with its examples 1-3, since the temperature of example 4 exceeds 500 ℃, the equivalent lifetime is significantly reduced, since the defect number of graphene, the preparation process has a direct effect on its temperature resistance stability in air, and thus the maximum use temperature of the material in air is 500 ℃ (short heating time).
The in-group comparison of comparative examples 10-12 shows that the short-term high temperature (500 ℃) resistance of the resin binder cannot be compared with that of the inorganic binder without adding flame retardant, and the high temperature working capacity can be ensured in a short time by adopting the high temperature resistant resin binder by optimizing the components, but the high temperature resistant resin binder is difficult to meet the requirement on maintaining the structural stability of the film layer when meeting the long-term high temperature working requirement.
Furthermore, it was found from comparative examples 1, 11, 8 and 9 that the graphene-supported nano-oxide has a decisive contribution in the film structure at a stable high temperature. The nano oxide ceramics used in comparative examples 8 and 9 are difficult to undergo a bonding reaction with the phosphate gum, so that it is difficult to maintain the integral structure of the film layer after dehydration and solidification of phosphate and discharge of PEO reaction during sintering, and pulverization occurs after cooling.
Likewise, comparison of example 2 with comparative example 10 shows that the volume change after dehydration and curing of the inorganic curing agent has a great influence on the stability of the film structure by thermal stress at high temperature.
In summary, the electrothermal film formed by the high-temperature electric heating slurry in the embodiment of the application can work in air at a high temperature of more than 400 ℃ for more than 3000 hours, so as to meet the requirement of high-temperature electric heating materials.
The foregoing is merely exemplary embodiments of the present application and is not intended to limit the scope of the present application, and various modifications and variations may be suggested to one skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (11)
1. The high-temperature electric heating slurry is characterized by comprising a solvent and components dispersed in the solvent, wherein the components comprise the following components in parts by weight: 5-15 parts of low-defect graphene, 4-18 parts of boron nitride, 3-13 parts of high-temperature-resistant curing agent and 4-20 parts of ceramic oxide, wherein the D50 particle size of the low-defect graphene is 10-15 mu m, and the D50 particle size of the boron nitride is 10-15 mu m;
in the Raman spectrum diagram of the low-defect graphene powder, the ratio of the D peak intensity to the G peak intensity is not more than 1/10, and the carbon-oxygen molar ratio in the low-defect graphene is not less than 20:1, a step of;
the high-temperature-resistant curing agent comprises phosphoric acid and aluminum dihydrogen phosphate;
the ceramic oxide is at least one of alumina and silica.
2. The high temperature electrically heated slurry of claim 1 wherein the low defect graphene has a mass loss rate of less than 2wt% calcined in air at 550 ℃ for 12 hours;
and/or the D50 particle size of the ceramic oxide is 10-40nm.
3. The high temperature electrically heated slurry of claim 1 wherein the mass ratio of the ceramic oxide to the low defect graphene is 1:2-14:3;
and/or the ceramic oxide is silicon oxide and aluminum oxide, the D50 granularity of the silicon oxide is 10-30nm, and the D50 granularity of the aluminum oxide is 20-40nm.
4. The high temperature electrically heated slurry of claim 1 wherein the high temperature resistant curing agent further comprises at least one of a silicate, a polyamideimide, a modified phenolic resin, and a modified polyimide.
5. The high temperature electric heating slurry according to claim 2, further comprising a dispersant dissolved in the solvent, the dispersant comprising at least one of hydroxyalkyl ethers, hydroxy isomeric alcohols, ethylene oxide, polyethylene glycol, dibasic acid esters, hydroxypropyl methylcellulose, polyvinylpyrrolidone.
6. The high temperature electric heating slurry according to claim 5, wherein the dispersant is a hydroxyalkyl ether or polyvinylpyrrolidone.
7. The high temperature electrically heated slurry of claim 1 wherein the solvent comprises at least one of deionized water, N-methylpyrrolidone.
8. A method for preparing the high-temperature electric heating paste according to any one of claims 1 to 7, comprising the steps of:
blending and sanding the low-defect graphene, the boron nitride, the ceramic oxide and the solvent;
and adding the high-temperature-resistant curing agent, and mixing to obtain the high-temperature-resistant curing agent.
9. The method for preparing a high-temperature electric heating paste according to claim 8, comprising the steps of:
uniformly mixing a dispersing agent and the solvent to obtain a composite base solution, adding low-defect graphene, boron nitride and ceramic oxide into the composite base solution, continuously stirring until the low-defect graphene, the boron nitride and the ceramic oxide are uniformly dispersed in the composite base solution, and sanding at a linear speed of 10-20m/s by taking zirconium balls with the diameter of 0.1-0.5mm as grinding media to obtain a dispersing solution;
adding the high-temperature-resistant curing agent into the dispersion liquid, and stirring at the speed of 200-500rpm for 1-3h at the temperature of 35-50 ℃.
10. An electric infrared heating film, which is mainly obtained by coating and curing the high-temperature electric heating slurry according to any one of claims 1 to 7.
11. The preparation method of the electric infrared heating film is characterized by comprising the following steps of:
applying the high temperature electric heating slurry according to any one of claims 1 to 7 to a substrate and drying and shaping at 40-70 ℃;
heating to 150-300 deg.c, maintaining for 0.3-1 hr, heating to 400-600 deg.c, maintaining for 0.5-2 hr, and sintering.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015103525A1 (en) * | 2014-01-06 | 2015-07-09 | Momentive Performance Materials Inc. | High aspect boron nitride, methods, and composition containing the same |
| CN110127682A (en) * | 2019-05-28 | 2019-08-16 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of graphene heat exchange film and preparation method thereof, graphene heat exchange coating and preparation method thereof, composite material |
| CN110256894A (en) * | 2019-06-18 | 2019-09-20 | 安徽工大化工科技有限公司 | A kind of modified graphene and preparation method thereof, a kind of watersoluble plumbago alkene heat radiation coating and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140077138A1 (en) * | 2012-09-10 | 2014-03-20 | William Marsh Rice University | Boron nitride-based fluid compositions and methods of making the same |
| KR101510806B1 (en) * | 2013-10-22 | 2015-04-08 | 현대자동차주식회사 | Coating layer of graphene oxide-ceramic hybrid, and method for preparing the same |
| CN103937298A (en) * | 2014-03-25 | 2014-07-23 | 东方电气集团东方汽轮机有限公司 | Inorganic heat dissipation paint and preparation method thereof |
| WO2017114174A1 (en) * | 2015-12-31 | 2017-07-06 | 济南圣泉集团股份有限公司 | Graphene electrothermal material and application thereof |
| JP6149147B1 (en) * | 2016-11-25 | 2017-06-14 | Ａｔｔａｃｃａｔｏ合同会社 | Framework forming agent and negative electrode using the same |
| CN108622887B (en) * | 2017-03-17 | 2020-04-14 | 郑州新世纪材料基因组工程研究院有限公司 | Method for preparing graphene through microwave puffing |
| CN108281216B (en) * | 2017-12-25 | 2020-08-04 | 常州二维碳素科技股份有限公司 | Water-based graphene high-temperature-resistant flame-retardant conductive paste and preparation method and application thereof |
| CN108532868B (en) * | 2018-02-27 | 2021-05-18 | 亚细亚建筑材料股份有限公司 | Composite slurry applied to decorative plate with heating function |
| CN113471412A (en) * | 2020-03-31 | 2021-10-01 | 北京卫蓝新能源科技有限公司 | Composite conductive slurry, preparation method, positive pole piece and lithium ion battery |
| CN113038642B (en) * | 2021-02-26 | 2022-09-09 | 西安华清烯能石墨烯科技有限公司 | Electric infrared heating film, preparation method thereof and electric infrared heating device |
| CN115175385A (en) * | 2022-07-28 | 2022-10-11 | 无锡辰海新材科技有限公司 | Water-soluble high-temperature-resistant infrared carbon-based heating slurry and preparation method thereof |
-
2022
- 2022-06-08 CN CN202210642897.2A patent/CN115029022B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015103525A1 (en) * | 2014-01-06 | 2015-07-09 | Momentive Performance Materials Inc. | High aspect boron nitride, methods, and composition containing the same |
| CN110127682A (en) * | 2019-05-28 | 2019-08-16 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of graphene heat exchange film and preparation method thereof, graphene heat exchange coating and preparation method thereof, composite material |
| CN110256894A (en) * | 2019-06-18 | 2019-09-20 | 安徽工大化工科技有限公司 | A kind of modified graphene and preparation method thereof, a kind of watersoluble plumbago alkene heat radiation coating and preparation method thereof |
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