CN115029022A - 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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- CN115029022A CN115029022A CN202210642897.2A CN202210642897A CN115029022A CN 115029022 A CN115029022 A CN 115029022A CN 202210642897 A CN202210642897 A CN 202210642897A CN 115029022 A CN115029022 A CN 115029022A
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Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- 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
-
- 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
- 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
-
- 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
- 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
-
- 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—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating 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—Heating 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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]
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Resistance Heating (AREA)
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 electrical heating slurry adopts low-defect graphene with high temperature resistance, the nano ceramic powder and the graphene with a large specific surface are compounded through a mechanical method, a cross-linking structure is formed by utilizing dehydration polycondensation reaction between phosphoric acid glue and the nano ceramic powder under an acidic condition, and the boron nitride nanosheet is matched to inhibit dimensional change and other means of the graphene caused by power-on heating, so that the structural stability and the working stability of the material at high temperature are improved. The boron nitride electric infrared heating film is mainly obtained by coating and curing the high-temperature electric heating slurry. The electric heating material provided by the embodiment of the application can work for more than 3000 hours at the high temperature of more than 400 ℃ in the air, and the requirement of the high-temperature electric heating material is met.
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
Since the carbon heating material, especially the heating material represented by the novel carbon materials such as graphene, carbon fiber and carbon crystal, has high electric-thermal conversion rate, and the infrared wavelength radiated during the operation can be widely applied to the application scenes such as food heating and human body heating, the carbon heating material has gained wide attention in the market and the heating product industry. Although various carbon heating coatings developed on the basis of conductive ink are easy to process into electric heating products with small heating film volume, high integration level and rapid temperature rise, the carbon heating products with the working temperature of more than 300 ℃ and corresponding material technologies are still in the development stage at present.
The current carbon heating material is difficult to be used as an electric heating material main body for long-term high-temperature work, and the reasons are mainly as follows: 1) most film-forming agents (binders) in the carbon heating coating are organic resin materials, and the mechanical properties of the coating are reduced in a cliff mode at a high temperature of more than 400 ℃ and react with oxygen in the air. 2) The volume change of the common inorganic curing agent can occur in the complete curing process and the temperature change process of hundreds of degrees centigrade, which causes the damage of the coating structure and the conductive loop formed by the carbon material, and further causes the open circuit of the electric heating material. 3) Most of carbon materials are easy to have irreversible redox reaction with air and other components in the coating under the high temperature environment of more than 400 ℃, so that the power is unstable and difficult to apply. 4) Most carbon materials change in volume and move thermally in the temperature change process of hundreds of degrees centigrade, which causes the change of a microscopic conductive system and further causes the instability of the conductivity of the coating.
Disclosure of Invention
The embodiment of the application aims to provide the high-temperature electric heating slurry, the electric infrared heating film and the preparation method, the electric heating material can work for more than 3000 hours at the high temperature of more than 400 ℃ in the air, and the requirement of the high-temperature electric heating material is met.
In a first aspect, an embodiment of the present application provides a high-temperature electrically heated slurry, which includes a solvent and components dispersed in the solvent, and the components include, 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 a Raman spectrogram of the low-defect graphene, the ratio of the intensity of a D peak to the intensity of a G peak is not more than 1/10, and the molar ratio of carbon to oxygen in the low-defect graphene is not less than 20: 1;
the high-temperature resistant curing agent comprises phosphoric acid and aluminum dihydrogen phosphate;
the ceramic oxide is at least one of alumina and silica.
In the technical scheme, the effective components in the high-temperature electric heating slurry consist 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 realizes the requirement of high-temperature electric heating under the combined action. The low-defect graphene has a special electronic structure and extremely high electron affinity, and has higher oxidation resistance compared with a common graphite-like structure carbon material; in addition, the single-layer/few-layer graphene has extremely high sheet-shaped geometrical structural characteristics under the sheet diameter of 10 microns, and a surface-to-surface overlapped conductive network link structure can be realized.
In addition, as the graphene generates thermal motion in the electrifying and heating process to damage a three-dimensional conductive network, ceramic powder is adopted for compounding, and then phosphoric acid glue reacts with the ceramic powder to form a phosphate-oxide ceramic curing system, so that unstable power and damage to a coating are avoided. The embodiment of the application adopts the boron nitride as the structural filler, has high heat conduction, low thermal expansion coefficient and stable structure, is a compact two-dimensional material, is favorable for improving the heat exchange efficiency inside and outside the film layer, and avoids the thermal stress damage to the film layer due to the large formation of the temperature difference inside and outside the film layer. Boron nitride finally ensures the structural stability and the working stability of the material at high temperature.
In one possible implementation, the D50 particle size of the low-defect graphene is 10-15 μm, and the mass loss rate of calcining at 550 ℃ for 12 hours in air is less than 2 wt%;
and/or the D50 particle size of the boron nitride is 10-15 μm.
And/or the ceramic oxide has a D50 particle size of 10-60 nm.
In one possible implementation manner, 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 particle size of the silicon oxide is 10-30nm, and the D50 particle size of the aluminum oxide is 20-40 nm.
In one possible implementation, the high temperature resistant curing agent further includes at least one of a silicate, a polyamide-imide, a modified phenolic resin, and a modified polyimide.
In one possible implementation, the method further comprises a dispersant dissolved in the solvent, wherein the dispersant comprises at least one of hydroxyalkyl ethers, hydroxyl isomeric alcohols, ethylene oxide, polyethylene glycol, dibasic esters, hydroxypropyl methyl cellulose and polyvinylpyrrolidone;
optionally, the dispersant is a hydroxyalkyl ether and polyvinylpyrrolidone.
In the technical scheme, due to the exposed surface electronic characteristics of the low-defect graphene, the common ionic dispersing agent has a poor dispersing effect on the graphene, and the adoption of the high-molecular dispersing agent as the main dispersing agent can cause coating flatulence easily caused when the high-molecular dispersing agent is adopted in a large amount at high temperature, so that a conductive loop formed by the graphene is damaged. The dispersant selected for use in the application is hydroxyalkyl ether with low saturated vapor pressure and matches with a small amount of high molecular surfactant (such as polyvinylpyrrolidone), so that most of the dispersant can be removed simultaneously with water in the low-temperature drying process while the graphene is effectively dispersed, and the coating is prevented from being damaged by flatulence 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 a high-temperature electrically heated slurry, which includes the following steps:
blending and sanding low-defect graphene, boron nitride, ceramic oxide and a solvent;
then adding a high-temperature resistant curing agent and mixing to obtain the product.
In the technical scheme, low-defect graphene, boron nitride, ceramic oxide and a solvent are blended and sanded to achieve the purposes of obtaining the proper particle size of the graphene, opening a graphene sheet layer, inserting boron nitride powder and compounding with ceramic oxide powder to form a bonding anchor point and dispersing all component powder; and adding a high-temperature resistant curing agent to form slurry, and preparing for a curing reaction.
In one possible implementation, it comprises the following steps:
uniformly mixing a dispersing agent and a solvent to obtain a composite base liquid, adding low-defect graphene, boron nitride and a ceramic oxide into the composite base liquid, continuously stirring until the low-defect graphene, the boron nitride and the ceramic oxide are uniformly dispersed in the composite base liquid, taking zirconium balls of 0.1-0.5mm as grinding media, and sanding at a linear speed of 10-20m/s to obtain a dispersion liquid;
adding a high-temperature-resistant curing agent into the dispersion, and stirring at the speed of 200-500rpm at 35-50 ℃ for 1-3 h.
In a third aspect, embodiments of the present application provide an electrical infrared heating film, which is mainly obtained by coating and curing the high-temperature electrical heating paste provided in the first aspect.
In a fourth aspect, embodiments of the present application provide a method for preparing an electrical infrared heating film, which includes the following steps:
coating the high-temperature electric heating slurry provided by the first aspect on a base material, and drying and shaping at 40-70 ℃;
firstly heating to 150-.
According to the technical scheme, after coating, drying and shaping are carried out at low temperature, the solvent and most of the auxiliary agent are discharged, the residual auxiliary agent is discharged by high-temperature sintering, the phosphoric acid glue is solidified, and the stress of the coating is released.
Detailed Description
The applicant finds that most of the curing agents (binders) used in the current large size sizing agent and paint vehicle are commonly used organic resin curing agents, and the organic resin materials have the following problems: the temperature resistance in the air is not enough, and the reaction with the air is easy; the glass transition temperature is low, and the mechanical performance is reduced in a cliff type at high temperature; thermal expansion and insufficient structural stability at high temperatures.
In addition, the electric heating material formed by several commonly used inorganic binders cannot stably work in an air environment of more than 400 ℃.
The glass powder is calcined at high temperature when used as a binder, and undergoes the processes of powder-softening-solidifying, the internal structure of the coating changes greatly and the strain is obvious in the two phase changes, and the carbon filler has high volume ratio, so that the film layer is easy to brittle fracture due to the obvious thermal expansion.
The dissolution of the silicate requires a strong alkaline environment, which is not beneficial to the dispersion of the graphene; water glass has similar problems to silicates.
The bonding strength of the pure-phase phosphate and the electric heating filler is insufficient, and the pure-phase phosphate is easy to pulverize after being sintered into a film.
After a great deal of research, the present inventors have found that a phosphoric acid gel (phosphoric acid + aluminum hydrogen phosphate) is used as a curing agent, and can react with graphene and a specific ceramic oxide (alumina and/or silica) to produce a high temperature resistant electric heating material, and phosphoric acid stabilizes an aluminum hydrogen phosphate component on the one hand and provides an acidic environment to allow a phosphate to react with alumina and/or silica to form a bond on the other hand. During the forming process of the slurry, along with the evaporation of the solvent, the concentration of the phosphoric acid glue is increased, and the phosphoric acid glue 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 clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The high-temperature electrically heated paste, the electric infrared heating film and the preparation method of the embodiment of the present application are specifically described below.
The embodiment of the application provides a 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 solvent.
Wherein, the main solvent is at least one of deionized water and N-methylpyrrolidone, and the mass ratio of the solvent is usually 60-75%.
In a Raman spectrogram 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 molar ratio of carbon to oxygen in the low-defect graphene is not less than 20: 1, the mass loss rate of calcining at 550 ℃ for 12 hours in air is less than 2 wt%. The low-defect graphene in the high-temperature electric heating slurry is powder, and the D50 particle size is 10-15 mu m.
The boron nitride in the high-temperature electric heating slurry in the embodiment of the application is powder, and the D50 granularity is 10-15 μm. 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 requirement.
The ceramic oxide in the embodiment of the present application refers to a ceramic oxide capable of reacting with the phosphoric acid glue, specifically, the ceramic oxide is at least one of alumina and silica; the ceramic oxide in the high-temperature electric heating slurry in the embodiment of the application is powder, and the D50 granularity is 10-60 nm. As an embodiment, the mass ratio of the ceramic oxide to the low-defect graphene is 1:2 to 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 particle size of the silicon dioxide is 10-30nm, and the D50 particle size of the aluminum oxide is 20-40 nm.
The dispersant comprises a slurry dispersant and a film dispersant; the slurry dispersing agent is selected from one or any combination of hydroxyalkyl ethers, hydroxyl isomeric alcohol, ethylene oxide, polyethylene glycol, dibasic acid ester, hydroxypropyl methyl cellulose and polyvinylpyrrolidone. As an embodiment, the dispersant includes hydroxyalkyl ethers and polyvinylpyrrolidone in a mass ratio of 3 to 6: 1.
the embodiment of the application also provides a preparation method of the high-temperature electric heating slurry, which comprises the following steps:
firstly, blending and sanding low-defect graphene, boron nitride, ceramic oxide, a dispersing agent and a solvent to obtain a dispersion liquid, and the specific process is as follows:
uniformly mixing a dispersing agent and a solvent to obtain a composite base liquid, adding low-defect graphene, boron nitride and a ceramic oxide into the composite base liquid, continuously stirring until the low-defect graphene, the boron nitride and the ceramic oxide are uniformly dispersed in the composite base liquid, taking zirconium balls of 0.1-0.5mm as grinding media, and sanding at a linear speed of 10-20m/s to obtain a dispersion liquid.
Secondly, adding a high-temperature resistant curing agent into the dispersion liquid, uniformly mixing, and specifically stirring at the speed of 200-50 ℃ and 500rpm for 1-3h to obtain the 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, and the thickness of the electric infrared heating film is generally 10-30 μm.
The embodiment of the application also provides a preparation method of the electric infrared heating film, which comprises the following steps:
(1) coating the high-temperature electric heating slurry on a base material, wherein the base material can be a quartz plate, and drying and shaping at 40-70 ℃.
(2) Firstly heating to 150-.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
This embodiment provides a high temperature electrically heated slurry, which is mainlyThe solvent consists of the following components in parts by weight: 8 parts of low-defect graphene, 12 parts of boron nitride micro-sheets, 12 parts of high-temperature-resistant curing agent and 15 parts of ceramic oxide. Wherein the D50 particle size of the low-defect graphene is 12 μm, the Raman spectrogram of the low-defect graphite has a 2D peak, and the distance between the 2D peak and the G peak is reduced by 5cm compared with the distance between the 2D peak and the G peak of 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 particle size of the boron nitride is 12 μm; the high-temperature resistant curing agent is phosphoric acid glue (the solid content is 40 wt%, and the main solvent is not included in the volatile part, which is not described in detail below); the ceramic oxide is nano silicon dioxide with D50 granularity of 20nm and nano aluminum oxide with D50 granularity of 30nm, and the proportion of the two is 1: 2.
the preparation method of the high-temperature electric heating slurry comprises the following steps:
(1) carrying out airflow crushing treatment on a low-defect graphene raw material 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 isomeric alcohol polyoxyethylene ether to 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, 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 are uniformly dispersed in the composite base solution, sanding at 20 ℃ by using a zirconium ball of 0.3mm as a grinding medium, and obtaining a low-defect graphene dispersion solution at a linear speed of 15 m/s; then, a high temperature resistant curing agent and a thickening agent (polyethylene oxide MW800 ten thousand) were added to the low defect graphene dispersion liquid, and then stirred at 40 ℃ at a speed of 300rpm for 2 hours to obtain a high temperature electrical heating slurry.
The solid content of the high-temperature electric heating slurry is 15.96 wt%, and the viscosity is 1600 Pa.s, wherein: the mass proportion of the dispersant is 3.16 percent (the mass proportion of the polyvinylpyrrolidone is 0.9 percent); the mass proportion of the main solvent is 75.36%; the mass percentage of the low-defect graphene powder is 3.01%; the mass percentage of boron nitride is 4.52%; the mass percentage 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 the electric infrared heating film is 10 μm, and the preparation method comprises the following steps:
(1) the high temperature electrically heated slurry of this example was applied to a quartz plate using a plate coater to form a coating, and dried at 60 ℃ for setting.
(2) And (3) putting the shaped flat plate into a muffle furnace, heating to 200 ℃ at the speed of 5 ℃/min, preserving heat for 30 minutes, heating to 500 ℃ at the speed of 2 ℃/min, preserving heat for 1 hour, and sintering to obtain the electric infrared heating film.
Example 2
The present embodiment provides a high-temperature electrically heated slurry, and the preparation method thereof is different from that of embodiment 1 in that:
(2) uniformly mixing a dispersing agent (dibasic acid ester and polyethylene glycol with MW of 200, liquid, the mass ratio of the dibasic acid ester to the polyethylene glycol being 9:1) and a main solvent (N-methyl pyrrolidone) to obtain a composite base liquid, then adding low-defect graphene powder, boron nitride and ceramic oxide into the composite base liquid, continuously stirring until the low-defect graphene powder, the boron nitride and the ceramic oxide (aluminum oxide) are uniformly dispersed in the composite base liquid, and then sanding at a linear speed of 15m/s by taking a zirconium ball of 0.3mm as a grinding medium at a temperature of 20 ℃ to obtain a low-defect graphene dispersion liquid; and then adding a high-temperature resistant curing agent (modified phenolic resin) and a dispersing agent (hydroxymethyl cellulose) into acetone to completely dissolve, then adding a dispersing solution, stirring at 40 ℃ for 30 minutes at the speed of 300rpm, then adding ethanol and a high-temperature resistant curing agent (phosphoric acid gum, the solid content is 40 wt%), and continuously stirring for 2 hours, wherein the mass ratio of acetone to ethanol to hydroxymethyl cellulose is 9: 1: 0.05, obtaining the high-temperature electric heating slurry.
The solid content of the high-temperature electric heating slurry is 14.58 wt%, and the viscosity is 1500 Pa.s, wherein: the mass ratio of the dispersing agent is 6.91% (wherein the mass ratio of the hydroxymethyl cellulose is 0.07%), the mass ratio of the main solvent is 61.6%, the mass ratio of the low-defect graphene powder is 3.42%, the mass ratio of the boron nitride is 2.74%, the mass ratio of the ceramic oxide is 2.74%, and the mass ratio of the high-temperature resistant curing agent is 8.9% of the mass of the film-making slurry (the mass ratio of the modified phenolic resin to the phosphoric acid glue is 5: 8).
This example also provides an electrical infrared heating film, which is prepared by the following method different from that of example 1: the high-temperature electrically heated paste of this example was applied to a substrate using a plate coater to obtain an electric infrared heating film having a thickness of 15 μm.
Examples 3 to 4
Each example provides a high temperature electrically heated paste and a corresponding electrical infrared heating film, respectively, which were prepared in substantially the same manner as in example 1.
In examples 1 to 4, the weight parts of low-defect graphene and ceramic oxide in the electric infrared heating film, 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 electrically heated pastes in examples 1-4 are shown in Table 2; the solid contents and viscosities of the electric infrared heating films, and the kinds of flat plate substrates used in examples 1 to 4 are shown in Table 3.
The low-defect graphene raw material in examples 1 to 4 was purchased from zhengzhou new materials science and technology limited and was graphene prepared by a physical puffing method; the modified phenolic resin is a commercial modified phenolic resin which can resist the temperature of 600 ℃ and is sold in the market; the phosphate gel is a mixture of aluminum dihydrogen phosphate, aluminum phosphate and concentrated phosphoric acid (solute accounts for about 40%); the electric infrared heating film is prepared by controlling the coating head and the coating stroke to prepare a rectangular coating of 80 x 100 mm. The parts not described in tables 1 to 3 are the same as those in the preparation method of example 1, and are not described again.
TABLE 1 slurry compositions for examples 1-4
TABLE 2 concrete compositions of slurries of examples 3-4
TABLE 3 slurries of examples 1-4, substrates employed and product parameters
Comparative examples 1 to 14
The comparative example 1 is a commercially available carbon fiber heating wire, and the test is carried out by destroying a quartz/glass tube body of a generally commercially available carbon fiber heating tube, only keeping a carbon fiber heating body and an electrode structure, and directly electrifying to heat up to 400 ℃.
Comparative example 2 is a commercial microcrystalline hot plate with a nominal operating temperature <260 ° (alda).
The electric infrared heating films of comparative examples 3 to 7 were manufactured by various commercially available carbon materials, and were different from example 1 only in the electric infrared heating film on the quartz plate: procedure for preparing an electric infrared heating film on a quartz plate of comparative examples 3 to 7 referring to the method for preparing an electric infrared heating film of example 1, except that comparative examples 3 to 7 remove only boron nitride micro-slabs or replace low-defect graphene with other carbon materials, as detailed in table 4, are not described to be identical to example 1.
Procedure for preparing an electric infrared heating film on a quartz plate of comparative examples 8 to 9 referring to the method for preparing an electric infrared heating film of example 1, the difference is that the ceramic oxide powder compounded with low-defect graphene is replaced with filler powders of titanium dioxide and zirconium oxide, respectively.
Procedure for producing the electric infrared heating film on the quartz plate of comparative examples 10 to 12 referring to the production method of the electric infrared heating film of example 1, except that the high temperature resistant curing agent used was replaced with water glass, aluminum phosphate and polyimide wet powder (40 wt%), respectively.
Procedure for preparing an electric infrared heating film on a quartz plate of comparative examples 13 to 14 referring to the method for preparing an electric infrared heating film of example 1, the difference is that polyvinylpyrrolidone and sodium polyacrylate are used as the dispersing agents.
TABLE 4 compositions of pastes corresponding to the electric infrared heating films of comparative examples 3 to 7 and the conditions after sintering of the coatings
The viscosity of the coating formed by the comparative examples 8-9 is less than 300 pas, and after the coating is sintered, the phenomena of pulverization and material dropping appear on the surface layer of the film layer. Because the integrity of the film layer is greatly damaged by sintering, the power-on test is not carried out under the safety consideration.
In comparative examples 10 to 12, after the coating was sintered, powder falling occurred on the surface of the film layer, and the integrity of the film layer was substantially intact, and the subsequent test experiments were performed after judgment.
Comparative examples 13-14, in which pinholes appeared in the film after the coating was sintered, the film remained substantially intact, and subsequent experiments were carried out.
Temperature resistance test in air environment
The resistance of the coatings of the comparative examples 3 to 5 is obviously improved in the sintering process in the air, and the color of the coatings is changed from black to grey, so that the coatings cannot bear the subsequent durability test under the condition of 400 ℃ and cannot be subjected to the temperature resistance test any more in the comparative examples 8 to 9, and the temperature resistance test objects of the experiments are the samples of the examples 1 to 4 and the comparative examples 1, 2, 6, 7 and 10 to 14.
The commercial products in comparative example 1 and comparative example 2 can be directly subjected to temperature rise and durability tests by connecting a constant voltage power supply, and the homemade electric infrared heating films in other examples and comparative examples are coated with silver paste in parallel along the short sides, then molybdenum sheet electrodes 15mm in width and 2mm in thickness are arranged, and the molybdenum sheet electrodes are connected with the power supply for testing.
Experimental example 1
The test specimens were subjected to 50Hz alternating current, the voltage was raised at a rate of 1V/min until the specimens were heated to 400 ℃ for 30 minutes and the voltage and power were recorded, the results being shown in Table 5.
Table 5 experimental results of examples and comparative examples in experimental example 1
As can be seen from table 5, the general commercially available carbon fiber heating body material of comparative example 1 was insufficient in stability when operated at 400 ℃ in air, and no longer subjected to the durability test for safety and necessity. The sealing material of the micro heater plate of comparative example 2 could not satisfy the long-term heating at 400 ℃. Compared with redox graphene, the thermal stability of the repaired graphene oxide adopted in the comparative example 6 in the air is greatly improved due to fewer defects; similarly, the low defect graphene mentioned in the present application was used in examples 1 to 4. The stability of all examples is good, confirming the importance of the 4 key elements proposed in this application with respect to the temperature resistant carbon material. Meanwhile, the comparison example 7 shows that the addition of the boron nitride micro-sheets has a significant effect on stabilizing the overall working stability of the material microstructure of the material in the temperature rise process, and the view of structural stability under thermal expansion in 4 key factors proposed in the application is verified again.
Experimental example 2
For the sample with better stability in the experimental example 1, the accelerated aging durability test of the overtemperature and overpower is carried out on the sample according to the conversion mode of the 22 nd item in GB/T7287-2008, the power attenuation is less than or equal to 5 percent as the life judgment index, the equivalent life of the sample is recorded at intervals of 12 hours, 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, it was found that the coating of comparative example 6 was burnt out at a certain point in the heat generation zone of the coating made of reduced graphene oxide after the first 12 hours.
The coating in comparative example 7 was clearly found to warp after breaking from a certain center point after the first 12 hours; the reason why the volume expansion rate of graphene is not consistent with the thermal expansion rate of the cured binder, the difference is large, and the internal structure of the electric heating material is unstable at high temperature for a long time to cause overheating of the material can be inferred by combining the surface pulverization phenomenon generated on the surface after the sintering process and the phenomenon of small power amplitude increase and the like in experimental example 1.
All of examples 1 to 4 exhibited equivalent lives of 4000 hours or more, and were judged to have practical value as heat-generating body materials.
By comparing example 4 with examples 1-3 thereof, it can be seen that the equivalent life is significantly reduced because the temperature of example 4 exceeds 500 ℃, because the number of defects of graphene and the preparation process have direct influence on the temperature resistance stability in air, and therefore the maximum use temperature of the material in air is 500 ℃ (short-time heating).
Comparison in groups of comparative examples 10 to 12 shows that the resin binder has short-term high temperature (500 ℃) resistance without adding a flame retardant, and the high temperature working capacity can be ensured in a short time by optimizing the components and adopting the high temperature resistant resin binder, but the high temperature resistant resin binder cannot meet the requirement on keeping the structural stability of a film layer when meeting the requirement of long-term high temperature working.
Furthermore, by laterally comparing example 1, comparative example 11, comparative example 8 and comparative example 9, it can be found that the graphene-supported nano-oxide has a decisive contribution in stabilizing the film layer structure at high temperature. The nano oxide ceramics adopted in the comparative examples 8 and 9 are difficult to generate bonding reaction with phosphoric acid glue, so that the integral structure of the film layer is difficult to maintain after dehydration and solidification of phosphate and PEO reaction discharge in the sintering process, and pulverization occurs after cooling.
Similarly, the comparison between example 2 and comparative example 10 shows that the volume change of the inorganic curing agent after dehydration and curing and the thermal stress at high temperature have great influence on the stability of the film structure.
In summary, the electric infrared heating film formed by the high-temperature electric heating slurry of the embodiment of the application can work in the air at a high temperature of more than 400 ℃ for more than 3000 hours, and the requirement of high-temperature electric heating materials is met.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
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;
in a Raman spectrogram of the low-defect graphene powder, the ratio of the intensity of a D peak to the intensity of a G peak is not more than 1/10, and the molar ratio of carbon to oxygen in the low-defect graphene is not less than 20: 1;
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.
2. The high-temperature electric heating slurry as claimed in claim 1, wherein the low-defect graphene has a D50 particle size of 10-15 μm, and a mass loss rate of less than 2 wt% after being calcined at 550 ℃ for 12 hours in air;
and/or the D50 particle size of the boron nitride is 10-15 μm;
and/or the ceramic oxide has a D50 particle size of 10-40 nm.
3. The high-temperature electrically heated slurry according to claim 1, wherein the mass ratio of the ceramic oxide to the low-defect graphene is 1:2 to 14: 3;
and/or the ceramic oxide is silicon oxide and aluminum oxide, the D50 particle size of the silicon oxide is 10-30nm, and the D50 particle size of the aluminum oxide is 20-40 nm.
4. A high temperature electrically heated paste as recited in 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. A high temperature electrically heated paste according to claim 2 further comprising a dispersant dissolved in said solvent, said dispersant comprising at least one of hydroxyalkyl ethers, hydroxy isomeric alcohols, ethylene oxide, polyethylene glycol, dibasic esters, hydroxypropyl methylcellulose, polyvinylpyrrolidone;
optionally, the dispersant is a hydroxyalkyl ether and polyvinylpyrrolidone.
6. A high temperature electrically heated paste according to claim 1 wherein said solvent comprises at least one of deionized water, N-methyl pyrrolidone.
7. A method for preparing a high temperature electrically heated paste according to any of claims 1 to 6, 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.
8. A method for preparing a high temperature electrically heated paste according to claim 7, characterised in that it comprises the steps of:
uniformly mixing a dispersing agent and the solvent to obtain a composite base solution, adding low-defect graphene, boron nitride and a 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 then sanding at a linear velocity of 10-20m/s by using zirconium balls of 0.1-0.5mm as a grinding medium to obtain a dispersion 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 ℃.
9. An electric infrared heating film, which is obtained by coating and curing mainly the high-temperature electric heating paste as claimed in any one of claims 1 to 6.
10. The preparation method of the electric infrared heating film is characterized by comprising the following steps:
coating the high-temperature electric heating slurry as claimed in any one of claims 1 to 6 on a substrate, and drying and shaping at 40-70 ℃;
firstly heating to 150-.
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