CN110519870B - Graphene/base metal alloy conductive material, resistance paste, heating element, preparation and application thereof - Google Patents
Graphene/base metal alloy conductive material, resistance paste, heating element, preparation and application thereof Download PDFInfo
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- CN110519870B CN110519870B CN201810491757.3A CN201810491757A CN110519870B CN 110519870 B CN110519870 B CN 110519870B CN 201810491757 A CN201810491757 A CN 201810491757A CN 110519870 B CN110519870 B CN 110519870B
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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
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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
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/017—Manufacturing methods or apparatus for heaters
Abstract
The invention belongs to the field of conductive materials, and particularly relates to a graphene/base metal alloy conductive material which is characterized by comprising graphene, alloy powder and glass powder. The invention also provides a conductive paste containing the conductive material; a heat-generating body containing the conductive material; the invention also provides a preparation method and application of the heating element. The conductive material has excellent performance, and the film heating body prepared from the conductive material has the advantages of good safety, low cost, good conductivity, strong binding force, high heating speed and the like, and is particularly suitable for being applied to a hair-waving rod.
Description
Technical Field
The invention relates to preparation and application of a stainless steel-based doped graphene alloy heating film, in particular to application of a stainless steel-based doped graphene alloy heating film heating body in a hair perming rod.
Background
With the problems of short service life, inflexible heating mode, low heating efficiency and the like reflected by the traditional heating mode, the traditional heating mode can not meet the existing requirements, electrothermal films are continuously produced as heating elements in recent years, and the thick film heating elements can be divided into ceramic bases, glass bases, polymer bases and metal bases according to base materials of the thick film heating elements, wherein the metal bases belong to stainless steel base materials and are the most widely used, and the stainless steel base heating elements have the advantages of large power density, small volume, convenience in installation, vibration resistance and the like. However, the stainless steel-based heating film has high requirements on the insulativity of the base material, and has high requirements on performance indexes such as heating speed, oxidation resistance, binding force and the like of the heating film. For example, the Chinese patent "electroconductive paste for high-power thick film circuit based on stainless steel substrate and its preparation process" (application number: 02139895.X) describes silver-palladium resistance paste printed stainless steel substrate as high-power circuit. Because the noble metal is adopted as the conductive phase, the production cost is greatly increased, and the oxidation resistance of the heating film is poor; silver is easy to migrate in the sintering process, and the insulation property of the stainless steel substrate is difficult to ensure. For example, the YBCO thick film resistor paste based on the stainless steel substrate and the preparation method thereof (application number: 201010158934) in Chinese patent introduces the YBCO thick film resistor based on the stainless steel substrate. Because the solid-phase synthesis of YBCO has the disadvantages of high cost, low purity, overhigh production cost, poor thermal expansion coefficient matching, poor conductive performance of a resistive film, influenced heating speed and the like. Therefore, there is an urgent need to find a thick film heating resistor material with low cost, good conductivity, high safety and fast heating speed.
Disclosure of Invention
In order to solve the defects of the prior art, a first object of the present invention is to provide a graphene/base metal alloy conductive material (also referred to as a conductive material or a conductive composition for short) and to provide a conductive material with good conductive performance.
The second purpose of the invention is to provide a doped graphene alloy resistance paste containing the graphene/base metal alloy conductive material.
The stainless steel thick film heating film aims at solving the defects of high cost, poor conductivity, poor binding force and low heating speed of the existing stainless steel base material thick film heating film. The third purpose of the invention is to provide a stainless steel-based doped graphene alloy heating film heating element which comprises the graphene/base metal alloy conductive material and has a completely new structural characteristic.
The fourth purpose of the invention is to provide a preparation method of the stainless steel-based doped graphene alloy heating film heating body.
The fifth purpose of the invention is to provide application of the stainless steel-based doped graphene alloy heating film heating body.
A graphene/base metal alloy conductive material comprises graphene, alloy powder and glass powder.
By adopting the conductive material, the raw materials and the production cost can be greatly reduced through the cooperation of the components; moreover, the conductive material can also contribute to the densification of the heating film sintered by the conductive material, reduce the defects of the heating film obtained by sintering and ensure that the heating film has higher stability. In addition, the base metal alloy is doped with graphene as a part of conductive phase, so that the conductive performance of the film can be greatly improved, and simultaneously, as the base metal alloy has a lamellar structure, the bonding strength between alloy conductive particles and a glass binder and between the alloy conductive particles and a dielectric layer is increased, and the doped graphene also plays a role in adjusting the thermal expansion of the film layer, so that the mechanical thermal shock resistance of the film layer is enhanced, the stability of the film is improved, and the service life of the heating element is prolonged.
Preferably, in the graphene/base metal alloy conductive material, the melting point of the glass powder is 600-800 ℃.
More preferably, the glass frit is microcrystalline glass.
More preferably, the solid phase component of the glass powder is SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3。
Preferably, the alloy powder is at least one of NiB, NiCu, NiFe and NiAlCr. The base metal alloy is adopted to replace noble metal, so that the cost of raw materials is reduced, and meanwhile, the sintering temperature can be reduced by matching the alloy with the graphene, so that the film can be sintered to be more compact, the defects are reduced, the process cost is reduced, and the stability of the film layer is improved.
More preferably, the alloy powder is NiB. Researches find that the synergistic effect of the NiB, the graphene and the glass is better, so that the resistance change caused by the thermal pressure generated by the film under hot stamping can be further reduced, and the stability of the film is greatly improved.
Preferably, the graphene is multilayer graphene, and the thickness of the graphene is 1 nm-100 nm. The graphene with the optimal thickness has a good synergistic effect with other components, and the conductivity of the film layer can be further synergistically regulated and controlled.
Preferably, in the graphene/base metal alloy conductive material, the weight part of alloy powder is 45-90 parts; 1-10 parts of graphene; the weight part of the glass powder is 1-15 parts. The effect is more excellent in the preferable range with the synergistic effect of the components being small.
The invention also provides a graphene alloy doped resistance paste which comprises the graphene/base metal alloy conductive material and an organic carrier.
Preferably, the organic vehicle comprises a solvent, a thickener, a thixotropic agent, a surfactant, and a binder.
The solvent is one or more of terpineol, diethylene glycol butyl ether acetate and dibutyl phthalate. Further preferably, the solvent is a mixture of terpineol, diethylene glycol butyl ether acetate and dibutyl phthalate.
The thickening agent can be conventional materials with thickening effect in the industry, and is preferably ethyl cellulose.
The thixotropic agent can be a conventional material with anti-thixotropy in the industry, and is preferably hydrogenated castor oil.
The surfactant can be conventional materials with surface activity improving performance in the industry, and is preferably oleic acid.
The binder may be a conventional material in the industry having enhanced viscosity, preferably polyvinyl butyral.
Preferably, in the organic carrier, the mass part ratio of the solvent, the thickening agent, the thixotropic agent, the surfactant and the binder is 85-93: 8-14: 1-4: 1-8.
Preferably, the organic carrier accounts for 10-30% of the doped graphene alloy resistance paste by mass. The balance being the graphene/base metal alloy conductive material.
Further preferably, in the doped graphene alloy resistance paste, by mass, 45% -90% of alloy powder, 1% -10% of graphene, 1% -15% of glass powder and 10% -30% of organic carrier.
The invention also provides a stainless steel-based graphene-doped alloy heating film heating body which comprises a stainless steel substrate, wherein two opposite planes of the stainless steel substrate are respectively compounded with an insulating heat conduction layer and a dielectric layer 1; a medium layer 2 is compounded on the surface of the medium layer 1; an alloy resistance layer is compounded on the surface of the dielectric layer 2; the surface of the alloy resistance layer is compounded with an insulating layer;
the alloy resistance layer contains the graphene/base metal alloy conductive material.
The invention provides a stainless steel-based doped graphene alloy heating film heating body with a brand new structure and innovative component advantages; the longitudinal section (the section perpendicular to the plane of the heating body) of the stainless steel-based doped graphene alloy heating film heating body is an insulating heat conduction layer, a stainless steel base material, a medium layer 1, a medium layer 2, an alloy resistance layer and an insulating heat insulation layer which are compounded in sequence.
The resistance material (slurry) is used as a heating film layer on the stainless steel base, so that the high-power use of the stainless steel base heating body can be met, strong thermal shock can be borne, the heating efficiency is high, and the use temperature is high. Moreover, the invention also innovatively adopts the composite dielectric layers (the dielectric layer 1 and the dielectric layer 2 which are sequentially compounded) to ensure that the base material, the dielectric layer and the alloy resistance layer are better subjected to thermal expansion cooperative matching, so that the combination strength and the stability of the base material are enhanced while the insulativity of the base material is increased.
Preferably, the alloy resistance layer is obtained by curing the doped graphene alloy resistance paste.
In the invention, the dielectric layer 1 contains glass 1, and the dielectric layer 2 contains glass 2;
the melting point of the glass 1 is 800-1000 ℃; the melting point of the glass 2 is 600-800 ℃.
According to the invention, through the use of the dielectric layer 1 and the dielectric layer 2 which are sequentially compounded, the base material, the dielectric layer and the alloy resistance layer can be better matched with the thermal expansibility, so that the bonding strength and the stability of the base material are enhanced while the insulativity of the base material is increased.
Preferably, the glass 1 is a glass-ceramic, and the solid phase component thereof is SiO2-Al2O3-CaO-MgO-B2O3。
Preferably, the glass 2 is a glass ceramics, and the solid phase component thereof is SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3。
The material of the insulating and heat conducting layer can adopt the material with insulating and heat conducting functions which is conventional in the industry.
The material of the insulating layer can be the conventional material with insulating and heat-insulating effects in the industry.
The top surface and the bottom surface of the heating body are provided with the coating insulating layer and the insulating heat conducting layer, so that the heat conversion efficiency of the heating body can be further improved.
The thickness of each layer can be adjusted according to the requirement, and preferably, the thickness of the dielectric layer 1 is 80-140 μm; the thickness of the dielectric layer 2 is 50-80 μm.
The invention also provides a preparation method of the stainless steel-based doped graphene alloy heating film heating body, which comprises the following steps:
the method comprises the following steps: pretreating the surface of a stainless steel substrate;
step two: mixing a solvent, a thickening agent, a thixotropic agent, a surfactant and a binder to obtain an organic carrier;
step three: mixing glass 1 and glass 2 with an organic carrier respectively to obtain medium slurry 1 and medium slurry 2 respectively;
step four: compounding the medium slurry 1 on one plane of the pretreated stainless steel substrate, drying, sintering and forming the medium layer 1 on the stainless steel substrate; then compounding the medium slurry 2 on the surface of the medium layer 1, drying and sintering to form the medium layer 2 on the surface of the medium layer 1;
step five: mixing alloy powder, graphene powder and glass powder to obtain the graphene/base metal alloy conductive material;
step six: mixing the graphene/base metal alloy conductive material with the organic carrier prepared in the second step to obtain the doped graphene alloy resistance slurry;
step seven: compounding the doped graphene alloy resistance slurry on the dielectric layer 2 in the fourth step, drying, sintering, and forming the alloy resistance layer (also referred to as a heating layer in the invention) on the dielectric layer 2;
step eight: spraying a layer of insulating slurry on the alloy resistance layer obtained in the step seven; and spraying a layer of insulating heat-conducting slurry on the opposite surface of the stainless steel substrate composite medium layer 1, and drying to obtain the stainless steel substrate doped graphene alloy heating film heating body.
The stainless steel base material is one of 430, 304 and 316.
In the preparation method, the organic carrier comprises a mixed solvent, a thickening agent, a thixotropic agent, a surfactant and a binder; wherein the mass part ratio of the solvent, the thickening agent, the thixotropic agent, the surfactant and the binder is 85-93: 8-14: 1-4: 1-8; the mixed solvent is one or more of terpineol, diethylene glycol butyl ether acetate and dibutyl phthalate.
The glass powder 1 is microcrystalline glass, and the solid phase component of the glass powder is SiO2-Al2O3-CaO-MgO-B2O3The glass powder 2 is microcrystalline glass, and the solid phase component is SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3。
Preferably, the glass powder of the graphene/base metal alloy conductive material and the glass 2 of the dielectric layer 2 are the same material.
The sintering process of the dielectric layer 1 in the fourth step comprises the following steps: in the air, the temperature is raised to 300-500 ℃ at the temperature raising rate of 2-10 ℃/min, the temperature is maintained for 1-5 h, then the temperature is raised to 800-1000 ℃ at the temperature raising rate of 0.5-10 ℃/min, and the temperature is maintained for 1-5 h.
The sintering process of the dielectric layer 2 comprises the following steps: in the air, the temperature is raised to 300-500 ℃ at the temperature raising rate of 2-10 ℃/min, the temperature is maintained for 1-5 h, then the temperature is raised to 600-800 ℃ at the temperature raising rate of 0.5-10 ℃/min, and the temperature is maintained for 1-5 h.
And fifthly, the alloy powder is one or more of NiB, NiCu, NiFe and NiAlCr.
And fifthly, the graphene is multilayer graphene, and the thickness of the graphene is 1 nm-100 nm.
According to the mass fraction, 45-90% of alloy powder, 1-10% of graphene, 1-15% of glass powder and 10-30% of organic carrier.
Seventhly, the sintering process of the alloy resistance layer comprises the following steps: at a vacuum degree of 10-4～10-3In Pa vacuum, the temperature is raised to 300-500 ℃ at the rate of 2-10 ℃/min, the temperature is maintained for 0.5-2 h, then the temperature is raised to 600-800 ℃ at the rate of 0.5-10 ℃/min, and the temperature is maintained for 0.5-3 h.
The invention relates to a more preferable stainless steel-based doped graphene alloy heating film heating body, and a preparation method thereof comprises the following steps:
the method comprises the following steps: and carrying out sand blasting treatment on the surface of the stainless steel substrate.
Step two: and uniformly mixing the mixed solvent, the thickening agent, the thixotropic agent, the surfactant and the binder to prepare the organic carrier.
Step three: and respectively and uniformly mixing the glass powder 1 and the glass powder 2 with the prepared organic carrier to obtain the medium slurry 1 and the medium slurry 2.
Step four: and respectively printing the medium paste 1 and the medium paste 2 on the pretreated stainless steel substrate in sequence by screen printing, drying and sintering to obtain the stainless steel substrate with the insulating layer.
Step five: and uniformly mixing the alloy powder, the graphene powder and the glass powder 2 to obtain mixed powder.
Step six: and D, uniformly mixing the mixed powder obtained in the fifth step with the organic carrier prepared in the second step to obtain the doped graphene alloy resistance slurry.
Step seven: printing the graphene alloy doped resistance paste on the stainless steel substrate in the fourth step according to a certain circuit pattern by screen printing, drying and sintering to obtain the stainless steel-based heating layer.
Step eight: and e, spraying a layer of insulating and heat-insulating slurry on the surface of the stainless steel composite coating obtained in the step seven, spraying a layer of insulating and heat-conducting slurry on the back surface of the stainless steel composite coating, and drying to obtain the stainless steel-based doped graphene alloy heating film heating body.
The invention also provides an application of the heating body, which comprises the application in a hair-waving rod.
The invention has the beneficial effects that:
(1) the functional phase adopts base metal alloy (NiB series), the difference between the conductivity and the conductivity of the noble metal is not large, so that the invention replaces the noble metal film, and the melting point of the alloy is lower than the sintering temperature of single metal, thereby reducing the sintering temperature of the heating film and greatly reducing the material and preparation cost.
(2) According to the invention, the graphene is doped in the alloy resistance paste, so that the electric conductivity of the heating film is increased, the heating speed is accelerated, the mechanical property of the film layer is increased, the bonding force between the heating film and the dielectric layer is enhanced, and the thermal shock resistance of the heating film is greatly improved.
(3) The invention adopts the microcrystalline glass with different gradient melting points as the stainless steel substrate composite dielectric layer, increases the insulating property of the substrate stainless steel, reduces the problem of poor thermal expansion coefficient matching among the substrate, the dielectric layer and the resistance layer, improves the binding force among the substrate, the dielectric layer and the resistance layer, and simultaneously improves the thermal shock resistance of the heating film and the safety performance of the heating element.
The resistivity of the heating element can reach 2.04 × 10-6 omega.m, and is improved by 27.8 times compared with the case without the structure and the conductive composition;
the insulation resistance of the heating element can reach 8G omega at most, and compared with a case without the structure and the conductive composition, the insulation resistance of the heating element is improved by 167%;
the heating speed of the heating element can reach 50 ℃/s at most, and compared with the case without the structure and the conductive composition, the heating element is increased by 116%;
the resistance change rate of the heat-resistant impact performance of the heating element can reach 1% at least, and compared with a case without the structure and the conductive composition, the resistance change rate of the heating element is reduced by 15 times;
the bonding strength between layers of the heating body is I grade, and compared with the case without the structure and the conductive composition, the bonding strength is improved by 2 grade;
drawings
FIG. 1 is a flow chart of the preparation of the stainless steel substrate composite dielectric layer of the invention
FIG. 2 is a flow chart of the preparation of a stainless steel-based graphene-doped alloy heating film heating element of the invention
FIG. 3 is a schematic structural diagram of a stainless steel-based graphene-doped alloy heating film heater according to the present invention;
in fig. 3, 1: insulating and heat insulating layer, 2: alloy resistance layer, 3: dielectric layers 2, 4: dielectric layers 1, 5: stainless steel base material, 6: an insulating heat conducting layer.
Detailed Description
The following examples were carried out in accordance with the operating methods described above:
in the following examples, the preparation process shown in fig. 1 was used for the stainless steel substrate composite dielectric layer.
The heat generating film heater in the following examples employed the manufacturing flow shown in FIG. 2.
The graphene is multilayer graphene, and the thickness of the graphene is 1 nm-100 nm.
The microcrystalline glass 1 is microcrystalline glass, and the solid phase component of the microcrystalline glass is SiO2-Al2O3-CaO-MgO-B2O3(ii) a The melting point is 800-1000 ℃;
the solid phase component of the microcrystalline glass 2 is SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3(ii) a The melting point is 600-800 ℃;
the insulating and heat-insulating coating is obtained by adopting the conventional insulating and heat-insulating coating, and the insulating and heat-insulating coating is a CN-302A material provided by Guangzhou Cannan New materials science and technology company;
the insulating heat-conducting coating is obtained by adopting the conventional insulating heat-conducting coating, and the insulating heat-conducting coating is, for example, CN-202A material provided by Guangzhou Cannan New materials science and technology Limited.
In the following examples, the heating element was produced according to the schematic view of the structure shown in FIG. 3; as shown in fig. 1, the heating element comprises a stainless steel substrate 5, and two opposite planes of the stainless steel substrate are respectively compounded with an insulating heat conduction layer 6 and a medium layer 1 (4); the surface of the dielectric layer 1(4) is compounded with a dielectric layer 2 (3); the surface of the dielectric layer 2(3) is compounded with an alloy resistance layer 2; the surface of the alloy resistance layer 2 is compounded with an insulating layer 1.
Example 1:
and carrying out sand blasting treatment on the surface of the 430 stainless steel substrate, wherein the sand blasting time is 30 min. According to the weight percentage of terpineol: the mixture required by the experiment is prepared by the weight portion ratio of the diethylene glycol butyl ether acetate to the dibutyl phthalate of 70: 20: 10
The solvent is used for preparing the organic carrier required by the experiment according to the weight part ratio of 85: 8: 1 of the mixed solvent, ethyl cellulose, polyvinyl butyral, hydrogenated castor oil and oleic acid. 40g of organic carrier and 60g of microcrystalline glass 1 are mixed and stirred for 2 hours, and then a three-roll grinder is used for repeatedly grinding for 5 times to obtain medium slurry 1. The medium paste 1 was printed on the surface of the 430 stainless steel substrate in a planar pattern by screen printing for 3 times, and finally the screen-printed sample was dried in a forced air drying oven at 80 ℃ for 1 hour. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 300 ℃ at the rate of 2 ℃/min, keeping the temperature for 1h, then heating to 800 ℃ at the rate of 0.5 ℃/min, and keeping the temperature for 1 h. And (3) mixing 40g of organic carrier and 60g of microcrystalline glass 2, stirring for 2h, and repeatedly grinding for 5 times by using a three-roll grinder to obtain the medium slurry 2. The medium slurry 2 is printed on the surface of the medium layer 1 in a planar pattern by screen printing for 3 times, and finally the screen-printed sample is placed into a forced air drying oven to be dried for 1h at the temperature of 80 ℃. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 300 ℃ at the heating rate of 2 ℃/min, preserving heat for 1h, heating to 600 ℃ at the heating rate of 0.5 ℃/min, and preserving heat for 1h to obtain the stainless steel-based composite dielectric layer.
Taking 45g of NiB alloy powder, 1g of graphene and 1g of microcrystalline glass powder 2, wherein the thickness of the graphene is 1nm, mixing, placing in a zirconia ball milling tank, adding a certain amount of absolute ethyl alcohol, mixing the powder material with the absolute ethyl alcohol to form paste, adding a certain amount of zirconia ball milling beads, wherein the ball material ratio is 1: 1, the large and medium small balls are 5: 3: 2, then placing in a ball mill for ball milling at 200r/min for 24 hours, filtering the material out of the zirconia ball milling tank, placing in a blast drying oven for drying, grinding the material into uniform powder, and sieving by a standard sieve of 100 meshes to obtain the alloy mixed powder.
Mixing and stirring 10g of organic carrier and 47g of alloy mixed powder for 2 hours, repeatedly grinding for 5 times by using a three-roll grinder to obtain doped graphene alloy resistance paste, printing the doped graphene alloy resistance paste on the doped graphene alloy resistance paste by a circuit with a pattern in a certain shape through screen printing for 5 times, and finally drying the silk-screened sample in a blast drying oven at 80 ℃ for 1 hour. After drying, taking out the sample and putting the sample into a vacuum furnace to sinter according to the following process: the vacuum degree is controlled at 10-4And in the Pa range, raising the temperature to 300 ℃ at the speed of 2 ℃/min, preserving the heat for 0.5h, then raising the temperature to 600 ℃ at the speed of 0.5 ℃/min, and preserving the heat for 0.5h to obtain the stainless steel-based heating film heating body. And finally, spraying an insulating heat-insulating coating on the surface of the heating film, spraying an insulating heat-conducting coating on the back surface of the stainless steel substrate, and drying in an air-blast drying oven at 80 ℃ for 1 h.
The stainless steel-based doped graphene alloy heating film heating element prepared in the example is subjected to a resistivity test, and the result shows that the heating film heating element has excellent conductivity, and the resistivity of the heating film heating element is 2.04 × 10-6Omega.m; for an insulation test, the insulation resistance is 8G omega; testing the heating rate of the heating film, wherein the result is that 7s reaches 300 ℃; the result of the test of the thermal shock resistance analysis test shows that the thermal cycle is 1000 times, the resistance value is changed by 1 percent, and the film is not oxidized; through adhesion fastness determination, the adhesion degrees of the film, the dielectric layer and the base material are I-grade, and the combination strength of the film, the dielectric layer and the base material is high.
Example 2:
and carrying out sand blasting treatment on the surface of the 304 stainless steel base material, wherein the sand blasting time is 30 min. According to the weight percentage of terpineol: preparing a mixed solvent required by the experiment according to the weight part ratio of the diethylene glycol butyl ether acetate to the dibutyl phthalate of 70: 20: 10, and preparing an organic carrier required by the experiment according to the weight part ratio of the mixed solvent to the ethyl cellulose to the polyvinyl butyral to the hydrogenated castor oil to the oleic acid of 93: 14: 4: 8. And (3) mixing and stirring 20g of organic carrier and 80g of microcrystalline glass 1 for 2 hours, and repeatedly grinding for 5 times by using a three-roll grinder to obtain the medium slurry 1. The medium paste 1 was printed on the surface of a 304 stainless steel substrate in a planar pattern by screen printing for 3 times, and finally the screen-printed sample was dried in a forced air drying oven at 80 ℃ for 1 hour. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 500 deg.C at a rate of 10 deg.C/min, maintaining for 5h, heating to 1000 deg.C at a rate of 10 deg.C/min, and maintaining for 5 h. And (3) mixing and stirring 20g of organic carrier and 80g of microcrystalline glass 2 for 2 hours, and repeatedly grinding for 5 times by using a three-roll grinder to obtain the medium slurry 2. The medium slurry 2 is printed on the surface of the medium layer 1 in a planar pattern by screen printing for 3 times, and finally the screen-printed sample is placed into a forced air drying oven to be dried for 1h at the temperature of 80 ℃. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 500 ℃ at the heating rate of 10 ℃/min, preserving heat for 5h, heating to 800 ℃ at the heating rate of 10 ℃/min, and preserving heat for 5h to obtain the stainless steel-based composite dielectric layer.
Taking 90g of NiCu alloy powder, 10g of graphene and 15g of microcrystalline glass powder 2, wherein the thickness of the graphene is 100nm, mixing, placing in a zirconia ball milling tank, adding a certain amount of absolute ethyl alcohol, mixing the powder material and the absolute ethyl alcohol into paste, adding a certain amount of zirconia ball milling beads, wherein the ball material ratio is 1: 1, the large and medium small balls are 5: 3: 2, then placing in a ball mill for ball milling at 200r/min for 24 hours, filtering the material out of the zirconia ball milling tank, placing in a blast drying oven for drying, grinding the material into uniform powder, and sieving by a standard sieve of 100 meshes to obtain the alloy mixed powder.
Mixing and stirring 30g of organic carrier and 115g of alloy mixed powder for 2 hours, repeatedly grinding for 5 times by using a three-roll grinder to obtain doped graphene alloy resistance paste, printing the doped graphene alloy resistance paste on the doped graphene alloy resistance paste by a circuit with a pattern in a certain shape through screen printing for 5 times, and finally drying the silk-screened sample in a blast drying oven at 80 ℃ for 1 hour. After drying, taking out the sample and putting the sample into a vacuum furnace to sinter according to the following process: the vacuum degree is controlled at 10-3And (3) in the Pa range, heating to 500 ℃ at the heating rate of 10 ℃/min, preserving the heat for 2h, then heating to 800 ℃ at the heating rate of 10 ℃/min, and preserving the heat for 3h to obtain the stainless steel-based heating film heating body. Finally, spraying an insulating heat-insulating coating on the surface of the heating film, spraying an insulating heat-conducting coating on the back of the stainless steel substrate, and putting air into the stainless steel substrateDrying at 80 deg.C for 1h in a drying oven.
The stainless steel-based doped graphene alloy heating film heating element prepared in the example is subjected to a resistivity test, and the result shows that the heating film heating element has excellent conductivity, and the resistivity of the heating film heating element is 4.12 × 10-6Omega.m; for an insulation test, the insulation resistance is 7.5G omega; testing the heating rate of the heating film, wherein the result is that 6s reaches 300 ℃; the result of the test of the thermal shock resistance analysis test shows that the thermal cycle is 1000 times, the resistance value is changed by 1 percent, and the film is not oxidized; through adhesion fastness determination, the adhesion degrees of the film, the dielectric layer and the base material are I-grade, and the combination strength of the film, the dielectric layer and the base material is high.
Example 3:
and carrying out sand blasting treatment on the surface of the 316 stainless steel base material, wherein the sand blasting time is 30 min. According to the weight percentage of terpineol: preparing a mixed solvent required by the experiment according to the weight part ratio of the diethylene glycol butyl ether acetate to the dibutyl phthalate of 70: 20: 10, and preparing an organic carrier required by the experiment according to the weight part ratio of the mixed solvent to the ethyl cellulose to the polyvinyl butyral to the hydrogenated castor oil to the oleic acid of 90: 10: 2: 4. And mixing and stirring 30g of organic carrier and 70g of microcrystalline glass 1 for 2 hours, and repeatedly grinding for 5 times by using a three-roll grinder to obtain the medium slurry 1. The medium paste 1 is printed on the surface of a 316 stainless steel substrate in a planar pattern by screen printing for 3 times, and finally the screen-printed sample is placed into a forced air drying oven to be dried for 1 hour at the temperature of 80 ℃. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 400 ℃ at the rate of 5 ℃/min, preserving heat for 3h, then heating to 900 ℃ at the rate of 5 ℃/min, and preserving heat for 3 h. And (3) mixing and stirring 30g of organic carrier and 70g of microcrystalline glass 2 for 2 hours, and repeatedly grinding for 5 times by using a three-roll grinder to obtain the medium slurry 2. The medium slurry 2 is printed on the surface of the medium layer 1 in a planar pattern by screen printing for 3 times, and finally the screen-printed sample is placed into a forced air drying oven to be dried for 1h at the temperature of 80 ℃. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 400 ℃ at the heating rate of 5 ℃/min, preserving heat for 3h, heating to 700 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3h to obtain the stainless steel-based composite dielectric layer.
Taking 70g of NiFe alloy powder, 5g of graphene and 7g of microcrystalline glass powder 2, wherein the thickness of the graphene is 50nm, mixing, placing in a zirconia ball milling tank, adding a certain amount of absolute ethyl alcohol, mixing the powder material with the absolute ethyl alcohol to form paste, adding a certain amount of zirconia ball milling beads, wherein the ball material ratio is 1: 1, the large and medium small balls are 5: 3: 2, then placing in a ball mill for ball milling at 200r/min for 24 hours, filtering the material out of the zirconia ball milling tank, placing in a blast drying oven for drying, grinding the material into uniform powder, and sieving by a standard sieve of 100 meshes to obtain the alloy mixed powder.
Mixing and stirring 15g of organic carrier and 82g of alloy mixed powder for 2h, repeatedly grinding for 5 times by using a three-roll grinder to obtain doped graphene alloy resistance paste, printing the doped graphene alloy resistance paste on the doped graphene alloy resistance paste by a circuit with a pattern in a certain shape through screen printing for 5 times, and finally drying the silk-screened sample in a blast drying oven at 80 ℃ for 1 h. After drying, taking out the sample and putting the sample into a vacuum furnace to sinter according to the following process: the vacuum degree is controlled at 10-3And (4) in the Pa range, raising the temperature to 400 ℃ at the rate of 4 ℃/min, preserving the heat for 1h, then raising the temperature to 700 ℃ at the rate of 5 ℃/min, and preserving the heat for 2h to obtain the stainless steel-based heating film heating body. And finally, spraying an insulating heat-insulating coating on the surface of the heating film, spraying an insulating heat-conducting coating on the back surface of the stainless steel substrate, and drying in an air-blast drying oven at 80 ℃ for 1 h.
The stainless steel-based doped graphene alloy heating film heating element prepared in the example is subjected to a resistivity test, and the result shows that the heating film heating element has excellent conductivity, and the resistivity of the heating film heating element is 3.22 × 10-6Omega.m; for an insulation test, the insulation resistance is 7.6G omega; testing the heating rate of the heating film, wherein the result is that 6s reaches 300 ℃; the result of the test of the thermal shock resistance analysis test shows that the thermal cycle is 1000 times, the resistance value is changed by 1 percent, and the film is not oxidized; through adhesion fastness determination, the adhesion degrees of the film, the dielectric layer and the base material are I-grade, and the combination strength of the film, the dielectric layer and the base material is high.
Example 4:
and carrying out sand blasting treatment on the surface of the 430 stainless steel substrate, wherein the sand blasting time is 30 min. According to the weight percentage of terpineol: preparing a mixed solvent required by the experiment according to the weight part ratio of the diethylene glycol butyl ether acetate to the dibutyl phthalate of 70: 20: 10, and preparing an organic carrier required by the experiment according to the weight part ratio of the mixed solvent to the ethyl cellulose to the polyvinyl butyral to the hydrogenated castor oil to the oleic acid of 88: 9: 3: 2: 5. Mixing and stirring 35g of organic carrier and 65g of microcrystalline glass 1 for 2 hours, and repeatedly grinding for 5 times by using a three-roll grinder to obtain the medium slurry 1. The medium paste 1 was printed on the surface of the 430 stainless steel substrate in a planar pattern by screen printing for 3 times, and finally the screen-printed sample was dried in a forced air drying oven at 80 ℃ for 1 hour. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 450 ℃ at the heating rate of 3 ℃/min, preserving heat for 4h, then heating to 850 ℃ at the heating rate of 8 ℃/min, and preserving heat for 2 h. And mixing and stirring 35g of organic carrier and 65g of microcrystalline glass 2 for 2 hours, and repeatedly grinding for 5 times by using a three-roll grinder to obtain the medium slurry 2. The medium slurry 2 is printed on the surface of the medium layer 1 in a planar pattern by screen printing for 3 times, and finally the screen-printed sample is placed into a forced air drying oven to be dried for 1h at the temperature of 80 ℃. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 350 ℃ at the heating rate of 6 ℃/min, preserving heat for 2h, heating to 750 ℃ at the heating rate of 2 ℃/min, and preserving heat for 4h to obtain the stainless steel-based composite dielectric layer.
Taking 60g of NiAlCr alloy powder, 3g of graphene and 5g of microcrystalline glass powder 2, wherein the thickness of the graphene is 35nm, mixing, placing in a zirconia ball milling tank, adding a certain amount of absolute ethyl alcohol, mixing the powder material and the absolute ethyl alcohol into paste, adding a certain amount of zirconia ball milling beads, wherein the ball-to-material ratio is 1: 1, wherein the large-to-medium ball ratio is 5: 3: 2, then placing in a ball mill for ball milling at 200r/min for 24 hours, filtering the material out of the zirconia ball milling tank, placing in a blast drying oven for drying, grinding the material into uniform powder, and sieving by a standard sieve of 100 meshes to obtain the alloy mixed powder.
Mixing and stirring 10g of organic carrier and 68g of alloy mixed powder for 2h, repeatedly grinding for 5 times by using a three-roll grinder to obtain doped graphene alloy resistance paste, printing the doped graphene alloy resistance paste on the mixed graphene alloy resistance paste by a circuit with a certain shape and pattern through screen printing,the printing times are 5 times, and finally the silk-screen printed sample is placed into a forced air drying oven to be dried for 1 hour at the temperature of 80 ℃. After drying, taking out the sample and putting the sample into a vacuum furnace to sinter according to the following process: the vacuum degree is controlled at 10-3And (4) in the Pa range, raising the temperature to 400 ℃ at the rate of 4 ℃/min, preserving the heat for 1h, then raising the temperature to 700 ℃ at the rate of 5 ℃/min, and preserving the heat for 2h to obtain the stainless steel-based heating film heating body. And finally, spraying an insulating heat-insulating coating on the surface of the heating film, spraying an insulating heat-conducting coating on the back surface of the stainless steel substrate, and drying in an air-blast drying oven at 80 ℃ for 1 h.
The stainless steel-based doped graphene alloy heating film heating element prepared in the example is subjected to a resistivity test, and the result shows that the heating film heating element has excellent conductivity, and the resistivity of the heating film heating element is 3.68 × 10-6Omega.m; for an insulation test, the insulation resistance is 7.3G omega; testing the heating rate of the heating film, wherein the result is that 8s reaches 300 ℃; the result of the test of the thermal shock resistance analysis test shows that the thermal cycle is 1000 times, the resistance value is changed by 1 percent, and the film is not oxidized; through adhesion fastness determination, the adhesion degrees of the film, the dielectric layer and the base material are I-grade, and the combination strength of the film, the dielectric layer and the base material is high.
Comparative example 1:
compared with the embodiment 1, the difference is that a dielectric layer 2 is not compounded on the surface of the dielectric layer 1, and the specific operation is as follows:
and carrying out sand blasting treatment on the surface of the 430 stainless steel substrate, wherein the sand blasting time is 30 min. According to the weight percentage of terpineol: preparing a mixed solvent required by the experiment according to the weight part ratio of the diethylene glycol butyl ether acetate to the dibutyl phthalate of 70: 20: 10, and preparing an organic carrier required by the experiment according to the weight part ratio of the mixed solvent to the ethyl cellulose to the polyvinyl butyral to the hydrogenated castor oil to the oleic acid of 85: 8: 1. 40g of organic carrier and 60g of microcrystalline glass 1 are mixed and stirred for 2 hours, and then a three-roll grinder is used for repeatedly grinding for 5 times to obtain medium slurry 1. The medium paste 1 was printed on the surface of the 430 stainless steel substrate in a planar pattern by screen printing for 3 times, and finally the screen-printed sample was dried in a forced air drying oven at 80 ℃ for 1 hour. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 300 ℃ at the heating rate of 2 ℃/min, preserving heat for 1h, heating to 800 ℃ at the heating rate of 0.5 ℃/min, preserving heat for 1h, and obtaining the stainless steel-based single medium layer.
Taking 45g of NiB alloy powder, 1g of graphene and 1g of microcrystalline glass powder 2, wherein the thickness of the graphene is 1nm, mixing, placing in a zirconia ball milling tank, adding a certain amount of absolute ethyl alcohol, mixing the powder material with the absolute ethyl alcohol to form paste, adding a certain amount of zirconia ball milling beads, wherein the ball material ratio is 1: 1, the large and medium small balls are 5: 3: 2, then placing in a ball mill for ball milling at 200r/min for 24 hours, filtering the material out of the zirconia ball milling tank, placing in a blast drying oven for drying, grinding the material into uniform powder, and sieving by a standard sieve of 100 meshes to obtain the alloy mixed powder.
Mixing and stirring 10g of organic carrier and 47g of alloy mixed powder for 2 hours, repeatedly grinding for 5 times by using a three-roll grinder to obtain doped graphene alloy resistance paste, printing the doped graphene alloy resistance paste on the doped graphene alloy resistance paste by a circuit with a pattern in a certain shape through screen printing for 5 times, and finally drying the silk-screened sample in a blast drying oven at 80 ℃ for 1 hour. After drying, taking out the sample and putting the sample into a vacuum furnace to sinter according to the following process: the vacuum degree is controlled at 10-4And in the Pa range, raising the temperature to 300 ℃ at the speed of 2 ℃/min, preserving the heat for 0.5h, then raising the temperature to 600 ℃ at the speed of 0.5 ℃/min, and preserving the heat for 0.5h to obtain the stainless steel-based heating film heating body. And finally, spraying an insulating heat-insulating coating on the surface of the heating film, spraying an insulating heat-conducting coating on the back surface of the stainless steel substrate, and drying in an air-blast drying oven at 80 ℃ for 1 h.
The stainless steel-based doped graphene alloy heat generating film heating element prepared in the comparative example was subjected to a resistivity test, and as a result, it showed excellent conductivity with a resistivity of 3.22 × 10-6Omega.m; for insulation test, the insulation resistance is 3G ℃; testing the heating rate of the heating film, wherein the result is that 7s reaches 300 ℃; the result of the test of the thermal shock resistance analysis test shows that the thermal cycle is 1000 times, the resistance value changes by 8 percent, and the film is not oxidized; through adhesion fastness determination, the adhesion degrees of the film, the dielectric layer and the base material are III-grade, and the low bonding strength is shown among the three.
Comparative example 2:
compared with the embodiment 1, the difference is that the resistive layer does not adopt the alloy, graphene and glass component system (the alloy is replaced by a single metal) required by the invention, and the specific operation is as follows:
and carrying out sand blasting treatment on the surface of the 430 stainless steel substrate, wherein the sand blasting time is 30 min. According to the weight percentage of terpineol: preparing a mixed solvent required by the experiment according to the weight part ratio of the diethylene glycol butyl ether acetate to the dibutyl phthalate of 70: 20: 10, and preparing an organic carrier required by the experiment according to the weight part ratio of the mixed solvent to the ethyl cellulose to the polyvinyl butyral to the hydrogenated castor oil to the oleic acid of 85: 8: 1. 40g of organic carrier and 60g of microcrystalline glass 1 are mixed and stirred for 2 hours, and then a three-roll grinder is used for repeatedly grinding for 5 times to obtain medium slurry 1. The medium paste 1 was printed on the surface of the 430 stainless steel substrate in a planar pattern by screen printing for 3 times, and finally the screen-printed sample was dried in a forced air drying oven at 80 ℃ for 1 hour. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 300 ℃ at the rate of 2 ℃/min, keeping the temperature for 1h, then heating to 800 ℃ at the rate of 0.5 ℃/min, and keeping the temperature for 1 h. And (3) mixing 40g of organic carrier and 60g of microcrystalline glass 2, stirring for 2h, and repeatedly grinding for 5 times by using a three-roll grinder to obtain the medium slurry 2. The medium slurry 2 is printed on the surface of the medium layer 1 in a planar pattern by screen printing for 3 times, and finally the screen-printed sample is placed into a forced air drying oven to be dried for 1h at the temperature of 80 ℃. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 300 ℃ at the heating rate of 2 ℃/min, preserving heat for 1h, heating to 600 ℃ at the heating rate of 0.5 ℃/min, and preserving heat for 1h to obtain the stainless steel-based composite dielectric layer.
Taking 45gNi metal powder, 1g of graphene and 1g of microcrystalline glass powder 2, wherein the thickness of the graphene is 1nm, mixing, placing in a zirconia ball milling tank, adding a certain amount of absolute ethyl alcohol, mixing the powder material with the absolute ethyl alcohol to form paste, adding a certain amount of zirconia ball milling beads, wherein the ball material ratio is 1: 1, the large ball to the medium ball ratio is 5: 3: 2, then placing in a ball mill for ball milling at 200r/min for 24 hours, filtering the material out of the zirconia ball milling tank, placing in a blast drying oven for drying, grinding the material into uniform powder, and sieving by a standard sieve of 100 meshes to obtain the metal mixed powder.
Mixing and stirring 10g of organic carrier and 47g of metal mixed powder for 2 hours, repeatedly grinding for 5 times by using a three-roll grinder to obtain doped graphene metal resistance paste, printing the doped graphene metal resistance paste on the mixed graphene metal resistance paste by a circuit with a pattern in a certain shape through screen printing for 5 times, and finally drying the silk-screened sample in a blast drying oven at 80 ℃ for 1 hour. After drying, taking out the sample and putting the sample into a vacuum furnace to sinter according to the following process: the vacuum degree is controlled at 10-4And in the Pa range, raising the temperature to 300 ℃ at the speed of 2 ℃/min, preserving the heat for 0.5h, then raising the temperature to 600 ℃ at the speed of 0.5 ℃/min, and preserving the heat for 0.5h to obtain the stainless steel-based heating film heating body. And finally, spraying an insulating heat-insulating coating on the surface of the heating film, spraying an insulating heat-conducting coating on the back surface of the stainless steel substrate, and drying in an air-blast drying oven at 80 ℃ for 1 h.
The stainless steel-based doped graphene metal heat generating film heater prepared in the comparative example was subjected to a resistivity test, and as a result, exhibited excellent conductivity having a resistivity of 4.67 × 10-6Omega.m; for an insulation test, the insulation resistance is 8G omega; testing the heating rate of the heating film, wherein the result is that 13s reaches 300 ℃; the result of the test of the thermal shock resistance analysis test shows that the thermal cycle is 1000 times, the resistance value changes by 15 percent, and the film is oxidized; through adhesion fastness determination, the adhesion degrees of the film, the dielectric layer and the base material are I-grade, and the combination strength of the film, the dielectric layer and the base material is high.
Comparative example 3:
compared with the embodiment 1, the main difference is that the resistance layer is not added with graphene, and the specific difference is as follows:
and carrying out sand blasting treatment on the surface of the 430 stainless steel substrate, wherein the sand blasting time is 30 min. According to the weight percentage of terpineol: preparing a mixed solvent required by the experiment according to the weight part ratio of the diethylene glycol butyl ether acetate to the dibutyl phthalate of 70: 20: 10, and preparing an organic carrier required by the experiment according to the weight part ratio of the mixed solvent to the ethyl cellulose to the polyvinyl butyral to the hydrogenated castor oil to the oleic acid of 85: 8: 1. 40g of organic carrier and 60g of microcrystalline glass 1 are mixed and stirred for 2 hours, and then a three-roll grinder is used for repeatedly grinding for 5 times to obtain medium slurry 1. The medium paste 1 was printed on the surface of the 430 stainless steel substrate in a planar pattern by screen printing for 3 times, and finally the screen-printed sample was dried in a forced air drying oven at 80 ℃ for 1 hour. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 300 ℃ at the rate of 2 ℃/min, keeping the temperature for 1h, then heating to 800 ℃ at the rate of 0.5 ℃/min, and keeping the temperature for 1 h. And (3) mixing 40g of organic carrier and 60g of microcrystalline glass 2, stirring for 2h, and repeatedly grinding for 5 times by using a three-roll grinder to obtain the medium slurry 2. The medium slurry 2 is printed on the surface of the medium layer 1 in a planar pattern by screen printing for 3 times, and finally the screen-printed sample is placed into a forced air drying oven to be dried for 1h at the temperature of 80 ℃. After drying, taking out the sample and putting the sample into a muffle furnace to sinter according to the following process: heating to 300 ℃ at the heating rate of 2 ℃/min, preserving heat for 1h, heating to 600 ℃ at the heating rate of 0.5 ℃/min, and preserving heat for 1h to obtain the stainless steel-based composite dielectric layer.
Mixing 45g of NiB alloy powder and 1g of microcrystalline glass powder 2, placing the mixture into a zirconia ball milling tank, adding a certain amount of absolute ethyl alcohol to mix the powder and the absolute ethyl alcohol into paste, adding a certain amount of zirconia ball milling beads with a ball-to-material ratio of 1: 1, wherein the large-medium ball ratio is 5: 3: 2, placing the mixture into a ball mill to perform ball milling at 200r/min for 24 hours, filtering the material out of the zirconia ball milling tank, placing the mixture into a blast drying oven to dry, grinding the dried material into uniform powder, and sieving the powder through a 100-mesh standard sieve to obtain alloy mixed powder.
Mixing and stirring 10g of organic carrier and 46g of alloy mixed powder for 2h, repeatedly grinding for 5 times by using a three-roll grinder to obtain alloy resistance paste, printing the alloy resistance paste on the alloy resistance paste by a circuit with a pattern in a certain shape through screen printing for 5 times, and finally drying the silk-screened sample in a blast drying oven at 80 ℃ for 1 h. After drying, taking out the sample and putting the sample into a vacuum furnace to sinter according to the following process: the vacuum degree is controlled at 10-4And in the Pa range, raising the temperature to 300 ℃ at the speed of 2 ℃/min, preserving the heat for 0.5h, then raising the temperature to 600 ℃ at the speed of 0.5 ℃/min, and preserving the heat for 0.5h to obtain the stainless steel-based heating film heating body.And finally, spraying an insulating heat-insulating coating on the surface of the heating film, spraying an insulating heat-conducting coating on the back surface of the stainless steel substrate, and drying in an air-blast drying oven at 80 ℃ for 1 h.
The stainless steel-based alloy heat generating film heat-generating body obtained in the comparative example was subjected to a resistivity test, and as a result, exhibited poor conductivity and had a resistivity of 6.04 × 10-5Omega.m; for an insulation test, the insulation resistance is 5.5G omega; testing the heating rate of the heating film, wherein the result is that 10s reaches 300 ℃; the result of the test of the thermal shock resistance analysis test shows that the thermal cycle is 1000 times, the resistance value is changed by 13 percent, and the film is not oxidized; the adhesion firmness is determined, the adhesion degree of the film and the dielectric layer is III grade, the adhesion degree of the dielectric layer and the base material is I grade, and the low bonding strength is shown among the three.
From examples 1 to 4, it can be seen that the stainless steel-based doped graphene alloy heating film has the advantages of good conductivity, high heating speed, high adhesion strength, good safety and the like.
It can be seen from the example 1 and the comparative examples 1 to 3 that if the doped graphene alloy of the present invention is not used as a functional phase and the microcrystalline glass having different gradient melting points of the present invention is not used as a stainless steel substrate composite dielectric layer, the formed heating film has the disadvantages of poor conductivity, slow heating speed and low efficiency of the heating film heating element, and the adhesion strength between the film and the dielectric layer, and between the dielectric layer and the substrate is seriously reduced.
While specific embodiments of the invention have been described above, it will be understood by those skilled in the art that these are by way of example only, and that various changes and modifications may be made thereto by those skilled in the art after reading the above disclosure, and equivalents may fall within the scope of the invention as defined by the appended claims.
Claims (16)
1. A stainless steel-based graphene alloy doped heating film heating body is characterized by comprising a stainless steel substrate, wherein two opposite planes of the stainless steel substrate are respectively compounded with an insulating heat conduction layer and a dielectric layer 1; a medium layer 2 is compounded on the surface of the medium layer 1; an alloy resistance layer is compounded on the surface of the dielectric layer 2; the surface of the alloy resistance layer is compounded with an insulating layer;
the alloy resistance layer contains a graphene/base metal alloy conductive material; the graphene/base metal alloy conductive material comprises graphene, alloy powder and glass powder;
the dielectric layer 1 contains glass 1, and the dielectric layer 2 contains glass 2;
the melting point of the glass 1 is 800-1000 ℃; the melting point of the glass 2 is 600-800 ℃.
2. The stainless steel-based doped graphene alloy heating film heating element as claimed in claim 1, wherein in the graphene/base metal alloy conductive material, the glass powder is microcrystalline glass, and the solid phase component of the glass powder is SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3-Bi2O3(ii) a The melting point is 600-800 ℃.
3. The stainless steel-based doped graphene alloy heating film heating element according to claim 1, wherein in the graphene/base metal alloy conductive material, the alloy powder is at least one of NiB, NiCu, NiFe, and nialr.
4. The stainless steel-based doped graphene alloy heating film heating element according to claim 1, wherein in the graphene/base metal alloy conductive material, the graphene is multilayer graphene, and the thickness is 1nm to 100 nm.
5. The stainless steel-based doped graphene alloy heating film heating element according to claim 1, wherein in the graphene/base metal alloy conductive material, the weight part of alloy powder is 45-90 parts; 1-10 parts of graphene; the weight part of the glass powder is 1-15 parts.
6. The stainless steel-based doped graphene alloy heating film heater according to claim 1, wherein the alloy resistance layer is obtained by curing a doped graphene alloy resistance paste;
the graphene alloy doped resistance paste comprises the graphene/base metal alloy conductive material and an organic carrier in the stainless steel-based graphene alloy doped heating film heater according to any one of claims 1 to 5.
7. The stainless steel-based doped graphene alloy heat-generating film heating element as claimed in claim 6, wherein the organic vehicle comprises a solvent, a thickener, a thixotropic agent, a surfactant and a binder.
8. The stainless steel-based doped graphene alloy heating film heating element according to claim 7, wherein in the organic carrier, the mass parts of the solvent, the thickener, the thixotropic agent, the surfactant and the binder are 85-93: 8-14: 1-4: 1-4: 1 to 8;
the organic carrier accounts for 10-30% of the mass percent of the doped graphene alloy resistance slurry;
the solvent is one or more of terpineol, diethylene glycol butyl ether acetate and dibutyl phthalate.
9. The stainless steel-based doped graphene alloy heating film heating element as claimed in claim 1, wherein the glass 1 is microcrystalline glass, and the solid phase component of the glass is SiO2-Al2O3-CaO-MgO-B2O3。
10. The stainless steel-based doped graphene alloy heating film heating element as claimed in claim 1, wherein the glass 2 is microcrystalline glass, and the solid phase component of the glass is SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3。
11. The preparation method of the stainless steel-based doped graphene alloy heating film heating element according to any one of claims 1 to 10, characterized by comprising the following steps:
the method comprises the following steps: pretreating the surface of a stainless steel substrate;
step two: mixing a solvent, a thickening agent, a thixotropic agent, a surfactant and a binder to obtain an organic carrier;
step three: mixing glass 1 and glass 2 with an organic carrier respectively to obtain medium slurry 1 and medium slurry 2 respectively;
step four: compounding the medium slurry 1 on one plane of the pretreated stainless steel substrate, drying, sintering and forming the medium layer 1 on the stainless steel substrate; then compounding the medium slurry 2 on the surface of the medium layer 1, drying and sintering to form the medium layer 2 on the surface of the medium layer 1;
step five: mixing alloy powder, graphene powder and glass powder to obtain the graphene/base metal alloy conductive material;
step six: mixing the graphene/base metal alloy conductive material with the organic carrier prepared in the second step to obtain the doped graphene alloy resistance slurry;
step seven: compounding the doped graphene alloy resistance slurry on the dielectric layer 2 in the fourth step, drying and sintering to form the alloy resistance layer on the dielectric layer 2;
step eight: spraying a layer of insulating slurry on the alloy resistance layer obtained in the step seven; and spraying a layer of insulating heat-conducting slurry on the opposite surface of the stainless steel substrate composite medium layer 1, and drying to obtain the stainless steel substrate doped graphene alloy heating film heating body.
12. The method of claim 11, wherein: the stainless steel base material is one of 430, 304 and 316.
13. The method of claim 11, wherein: in the fourth step, the sintering process of the dielectric layer 1 comprises the following steps: in the air, the temperature is raised to 300-500 ℃ at the temperature raising rate of 2-10 ℃/min, the temperature is maintained for 1-5 h, then the temperature is raised to 800-1000 ℃ at the temperature raising rate of 0.5-10 ℃/min, and the temperature is maintained for 1-5 h.
14. The method of claim 11, wherein: the sintering process of the dielectric layer 2 comprises the following steps: in the air, the temperature is raised to 300-500 ℃ at the temperature raising rate of 2-10 ℃/min, the temperature is maintained for 1-5 h, then the temperature is raised to 600-800 ℃ at the temperature raising rate of 0.5-10 ℃/min, and the temperature is maintained for 1-5 h.
15. The method of claim 11, wherein: in the seventh step, the sintering process of the alloy resistance layer comprises the following steps: at a vacuum degree of 10-4～10-3In Pa vacuum, the temperature is raised to 300-500 ℃ at the rate of 2-10 ℃/min, the temperature is maintained for 0.5-2 h, then the temperature is raised to 600-800 ℃ at the rate of 0.5-10 ℃/min, and the temperature is maintained for 0.5-3 h.
16. An application of the heat-generating body described in any one of claims 1 to 10 or the heat-generating body produced by the production method described in any one of claims 11 to 15, characterized in that: the application includes application in a rod for permanent wave.
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| CN107396466A (en) * | 2017-07-03 | 2017-11-24 | 王克政 | Electric slurry and preparation method thereof, thick film circuit chip thermal source and preparation method thereof |
| CN107979880A (en) * | 2017-12-19 | 2018-05-01 | 广东美的厨房电器制造有限公司 | Thick film heating plate and there is its electric steam box |
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