CN116970899B - Composite carbon-based resistor film and preparation method and application thereof - Google Patents
Composite carbon-based resistor film and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 98
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical group C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 44
- 230000005855 radiation Effects 0.000 claims abstract description 27
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
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- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
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- 229920000647 polyepoxide Polymers 0.000 claims description 5
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- 239000010439 graphite Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
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- 239000010410 layer Substances 0.000 description 88
- 239000006229 carbon black Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
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- 238000005137 deposition process Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
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- 238000001291 vacuum drying Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
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- 239000012808 vapor phase Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
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- 241001391944 Commicarpus scandens Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a composite carbon-based resistor film, a preparation method and application thereof, wherein the composite carbon-based resistor film consists of a bottom structural layer and a top compact layer which are sequentially arranged from bottom to top; the top compact layer is a fullerene film; the bottom structural layer is composed of a carbon-based conductive agent and a polymer binder; the fullerene film adopts fullerene C 60 、C 70 、C 76 、C 78 、C 80 、C 84 At least one of them. The preparation method comprises the following steps: providing a carbon-based conductive agent and a polymer binder, and uniformly mixing; adopting printing or knife coating or spraying to prepare the uniformly mixed carbon-based conductive agent and polymer binder into a bottom structural layer; and preparing a top compact layer on the bottom structural layer by adopting ultraviolet radiation auxiliary gas-phase vacuum thermal evaporation, and obtaining the composite carbon-based resistor film. Through the scheme, the wear-resistant and moisture-resistant ultraviolet radiation-resistant sensor has excellent wear resistance, moisture resistance and ultraviolet radiation resistance, and has high practical value and popularization value in the technical field of displacement sensors.
Description
Technical Field
The invention relates to the technical field of displacement sensors, in particular to a composite carbon-based resistor film, a preparation method and application thereof.
Background
The carbon-based conductive plastic angular displacement sensor takes the carbon-based resistance film as a core element, and the excellent performance of the carbon-based resistance film in the aspects of electric, process, mechanical and the like endows the displacement sensor with the advantages in the aspects of precision, service life, output smoothness, resolution and the like. The carbon-based conductive film is also called electrothermal carbon film, low-resistance conductive film and conductive carbon film. Generally, a carbon-based resistive film is formed by forming a single layer of a carbon-based film on a surface of a substrate, wherein the carbon-based film is formed of a carbon-based conductive agent and a polymer binder.
However, in practical applications, carbon-based resistive films have several drawbacks: (1) The surface of the carbon-based resistor film is easy to generate fatigue wear after being rubbed by the reciprocating motion of the brush contact; (2) The micro/nano-scale pores on the surface of the carbon-based resistor film can be used as transmission diffusion channels of water molecules in air to cause internal structure degradation; (3) The binder on the surface of the carbon-based resistive film undergoes chemical bond cleavage under ultraviolet radiation to cause surface structural degradation. Therefore, the performances of the carbon-based resistor film such as abrasion resistance, moisture resistance, ultraviolet radiation resistance and the like directly limit the performances of the displacement sensor in various aspects such as precision, service life, output smoothness, resolution and the like.
Conventional carbon black powders can be classified into gaseous carbon black and furnace carbon black. Wherein, the surface of the gas method carbon black contains a large number of carboxyl functional groups, and the pH value of the powder is about 4. In addition, the surface of the furnace carbon black contains a large amount of quinone functional groups, and the pH value of the powder is about 9. In the whole, the carbon black surface contains a large amount of carboxyl, phenol, lactone, quinone, anhydride and ether functional groups, and has certain hygroscopicity. Typically, the polymeric binder structure is composed of a main carbon chain and branched functional groups. The branched functional groups have certain instability characteristics due to: (1) cleavage of chemical bonds readily occurs under ultraviolet light; (2) hygroscopic expansion is likely to occur in a high humidity environment. Therefore, carbon-based resistive films composed of carbon black powder and a polymer binder exhibit a defect of excessive fluctuation in resistance value under ultraviolet light and high humidity environments.
At present, the unique positive curvature carbon cage structure of the fullerene endows the fullerene with typical characteristics: (1) the molecular structure of all carbon has stronger hydrophobicity; (2) The cage-shaped molecular structure has stronger strain energy absorptivity; (3) The hybridization degree of carbon atoms is between graphite sp2 and diamond sp3, and the ultraviolet light absorption is strong. Under ultraviolet radiation, fullerene molecules can undergo partial ring-opening reaction to form fullerene polymers, which is helpful for improving the wear resistance and water resistance of the fullerene polymers as film materials. Therefore, the fullerene can be used as a functional film material for wear resistance, water resistance and ultraviolet radiation filtering, and further applied to the fields of electronic components and the like.
Although fullerenes and derivatives thereof have been used in the field of sensors (e.g., strain/gas sensors, electrochemical sensors, optical sensors, etc.) as functional materials by liquid phase methods, the intrinsic mechanism thereof is to convert interactions between fullerenes and derivatives thereof and substances to be detected into physical signals for detecting various types of substances (e.g., gases, volatile organic compounds, metal ions, anions, biomolecules, etc.). However, there are a number of disadvantages to the use of the above fullerenes and their derivatives: (1) The solubility of fullerene in organic solvents is high, but the solvents have dissolution effect on other polymer-based films, which limits the application scenario of liquid phase method; (2) The fullerene has a low gasification temperature, so that vacuum vapor deposition film formation can be realized, but the fullerene molecules in the film prepared by a vapor phase method are simply physically stacked and cannot form chemical bond connection, so that the mechanical properties of the film prepared by the vapor phase method are limited. The analysis shows that the advantages of the fullerene vapor phase method film forming are combined, chemical bonding between fullerene molecules is realized, and the application of the fullerene and the derivative thereof in the sensor field can be promoted.
Therefore, it is highly desirable to provide a composite carbon-based resistor film, and a preparation method and application thereof, wherein the composite carbon-based resistor film uses a fullerene film as a compact layer to be modified on the surface of a conventional carbon-based resistor film, so that the composite carbon-based resistor film forming a top compact layer/bottom structural layer can effectively improve the wear resistance, moisture resistance and ultraviolet radiation resistance of the original carbon-based resistor film.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a composite carbon-based resistor film and a preparation method and application thereof, and adopts the following technical scheme:
a composite carbon-based resistor film consists of a bottom structural layer and a top compact layer which are sequentially arranged from bottom to top; the top compact layer is a fullerene film; the bottom structural layer is composed of a carbon-based conductive agent and a polymer binder; the fullerene film adopts fullerene C 60 、C 70 、C 76 、C 78 、C 80 、C 84 At least one of (a) and (b);
the mass ratio of the carbon-based conductive agent to the polymer binder is 10-40: 60 to 90 percent.
Further, the carbon-based conductive agent is at least one of graphite, graphene, carbon nanotube, carbon fiber, fullerene and amorphous carbon.
Further, the polymer binder is at least one of phenolic resin, epoxy resin, polyurethane resin, acrylic resin, vinyl acid resin and nitrile resin.
Further, the thickness of the bottom structural layer is 5-500 μm; the thickness of the top compact layer is 5-1000 nm.
A method for preparing a composite carbon-based resistive film, comprising the steps of:
providing a carbon-based conductive agent and a polymer binder, and uniformly mixing;
adopting printing or knife coating or spraying to prepare the uniformly mixed carbon-based conductive agent and polymer binder into a bottom structural layer;
and preparing a top compact layer on the bottom structural layer by adopting ultraviolet radiation auxiliary gas-phase vacuum thermal evaporation, and obtaining the composite carbon-based resistor film.
Further, the preparation of the bottom structural layer comprises the following steps:
dispersing the polymer binder in a dissolving agent, heating to 80 ℃, and completely dissolving the polymer binder; adding a carbon-based conductive agent, and performing ultrasonic dispersion for 1h at room temperature to obtain carbon-based resistance slurry for later use;
and (3) coating the carbon-based resistance paste on the surface of the epoxy glass fiber laminated board substrate by adopting printing, knife coating or spraying, and heating and drying to obtain the bottom structural layer.
Further, the preparation of the top dense layer comprises the following steps:
bottom structural layer and fullerene C 60 、C 70 、C 76 、C 78 、C 80 、C 84 At least one of which is placed in the closed cavity to be sealedThe pressure of the closed cavity is reduced to 5 multiplied by 10 -4 Pa, holding for 30min;
fullerene C 60 、C 70 、C 76 、C 78 、C 80 、C 84 Heating to 450-700 ℃, adopting ultraviolet radiation, and depositing on the bottom structural layer to obtain a top compact layer with the thickness of 5-1000 nm.
Further, the deposition rate on the bottom structural layer is 0.01-1nm/s.
Further, the ultraviolet radiation has an intensity of 10-200mW/cm -2 。
Use of a composite carbon-based resistive film in a displacement sensor.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the surface of carbon black and the branched chain of the polymer binder usually contain hygroscopic functional groups, and the fullerene molecules have an all-carbon structure, so that the hygroscopicity of the carbon-based resistor film can be effectively reduced, and the structural damage of the bottom structural layer caused by the permeation of water molecules is reduced. The ultraviolet radiation absorption characteristics of the fullerene molecules can reduce the structural damage of the bottom structural layer caused by ultraviolet radiation because the molecular structure of the polymer binder is easy to break through chemical bonds under ultraviolet radiation. Because the carbon black and the polymer binder are distributed on the surface of the film in a two-phase form, fatigue wear is easy to occur, the fullerene molecules have the advantages of high hardness, high elastic modulus, low friction coefficient and the like, and the wear resistance of the film is improved by polymerization reaction under ultraviolet radiation. Therefore, compared with the carbon-based resistor film formed by the conventional carbon black and the polymer adhesive, the composite carbon-based resistor film with the fullerene compact layer formed on the surface can effectively improve the wear resistance, the moisture resistance and the ultraviolet radiation resistance. In conclusion, the wear-resistant, moisture-resistant and ultraviolet radiation-resistant composite material has excellent wear resistance, moisture resistance and ultraviolet radiation resistance, and has high practical value and popularization value in the technical field of displacement sensors.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, the drawings to be used in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and should not be considered as limiting the scope of protection, and other related drawings may be obtained according to these drawings without the need of inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a top dense layer deposition apparatus of the present invention.
FIG. 2 shows fullerene C of the present invention 60 Ultraviolet visible absorption spectrum of the top dense layer.
FIG. 3 shows fullerene C of the present invention 60 Profile of the effect of the top dense layer on contact angle.
FIG. 4 shows fullerene C of the present invention 70 Ultraviolet visible absorption spectrum of the top dense layer.
FIG. 5 shows fullerene C of the present invention 70 Profile of the effect of the top dense layer on contact angle.
FIG. 6 shows fullerene C of the present invention 60 The stability of the top dense layer on contact resistance affects the profile.
Fig. 7 is a surface topography of a bottom structural layer of the present invention.
FIG. 8 is a surface topography of the top dense layer of the present invention.
FIG. 9 shows fullerene C of the present invention 70 The stability of the top dense layer on contact resistance affects the profile.
Detailed Description
For the purposes, technical solutions and advantages of the present application, the present invention will be further described with reference to the accompanying drawings and examples, and embodiments of the present invention include, but are not limited to, the following examples. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
In this embodiment, the term "and/or" is merely an association relationship describing the association object, and indicates that three relationships may exist, for example, a and/or B may indicate: a exists alone, A and B exist together, and B exists alone.
The terms first and second and the like in the description and in the claims of the present embodiment are used for distinguishing between different objects and not for describing a particular sequential order of objects. For example, the first target object and the second target object, etc., are used to distinguish between different target objects, and are not used to describe a particular order of target objects.
In the embodiments of the present application, words such as "exemplary" or "such as" are used to mean serving as examples, illustrations, or descriptions. Any embodiment or design described herein as "exemplary" or "for example" should not be construed as preferred or advantageous over other embodiments or designs. Rather, the use of words such as "exemplary" or "such as" is intended to present related concepts in a concrete fashion.
In the description of the embodiments of the present application, unless otherwise indicated, the meaning of "a plurality" means two or more. For example, the plurality of processing units refers to two or more processing units; the plurality of systems means two or more systems.
Example 1
As shown in fig. 1 to 3, the present embodiment provides a composite carbon-based resistive film and a method for manufacturing the same, the composite carbon-based resistive film being composed of a bottom structural layer and a top dense layer, which are sequentially arranged from bottom to top; the top compact layer is a fullerene film; the bottom structural layer is comprised of a carbon-based conductive agent and a polymeric binder.
In this embodiment, the preparation process of the bottom structural layer is as follows:
(1) 600mg of phenolic resin was dispersed in 1.5g of a mixed solvent of ethers and ketones, and heated to 80℃to dissolve the phenolic resin completely.
(2) 400mg of carbon black powder (i.e., amorphous carbon, KB 300) was dispersed in the ether-ketone mixed solvent of the phenolic resin, and the carbon-based resistor paste was prepared after ultrasonic dispersion at room temperature for 1 hour.
(3) And (3) coating the carbon-based resistor paste on the surface of the substrate by using screen printing equipment, heating to 170 ℃ by using a blast drying oven and keeping for 12 hours, finishing primary drying, and heating to 60 ℃ by using a vacuum drying oven and keeping for 12 hours to finish preparation of the bottom structural layer.
In this example, the top dense layer was prepared as follows:
as shown in FIG. 1, (1) sample the bottom structural layer and fullerene C 60 Placing in a closed cavity, and reducing the pressure in the closed cavity to 5×10 -4 Pa, and hold for 30min.
(2) By incorporating fullerenes C 60 Heating to 600 ℃, and monitoring by using a crystal oscillator film thickness meter, wherein the deposition rate is about 0.05nm/s.
(3) The ultraviolet intensity of the ultraviolet radiation system device is set to be 50mW/cm -2 And stopping the deposition process when the deposition thickness reaches 100nm by using a crystal oscillator film thickness meter to obtain a top compact layer.
As shown in FIG. 2, fullerene C 60 The top dense layer has a pronounced absorption peak in the ultraviolet spectral range, which is advantageous in reducing structural degradation of the bottom structural layer by exposure to ultraviolet radiation. As shown in FIG. 3, fullerene C 60 After the top compact layer is modified on the bottom structural layer, the contact angle of water on the surface of the film is increased from 21 degrees to 73 degrees, which is beneficial to reducing the degradation of the bottom structural layer caused by water vapor permeation after the bottom structural layer absorbs moisture.
Example 2
The embodiment provides a composite carbon-based resistor film and a preparation method thereof, wherein the composite carbon-based resistor film consists of a bottom structural layer and a top compact layer which are sequentially arranged from bottom to top; the top compact layer is a fullerene film; the bottom structural layer is comprised of a carbon-based conductive agent and a polymeric binder.
In this embodiment, the preparation process of the bottom structural layer is as follows:
(1) 600mg of phenolic resin was dispersed in 1.5g of a mixed solvent of ethers and ketones, and heated to 80℃to dissolve the phenolic resin completely.
(2) 350mg of VXC72 carbon black powder (i.e. amorphous carbon) and 20mg of multi-wall carbon nano tubes are dispersed in the mixed solvent of ethers and ketones of the phenolic resin, and the carbon-based resistor paste is prepared after ultrasonic dispersion for 1h at room temperature.
(3) And (3) coating the carbon-based resistor paste on the surface of the substrate by using screen printing equipment, heating to 170 ℃ by using a blast drying oven and keeping for 12 hours, finishing primary drying, and heating to 60 ℃ by using a vacuum drying oven and keeping for 12 hours to finish preparation of the bottom structural layer.
In this example, the top dense layer was prepared as follows:
as shown in FIG. 1, (1) sample the bottom structural layer and fullerene C 70 Is placed in a closed cavity, and the pressure in the closed cavity is reduced to 5 multiplied by 10 by a vacuum system device -4 Pa, and hold for 30min.
(2) Fullerene C using heating system device 70 Heating to above 600 ℃, and monitoring the deposition rate to about 0.1nm/s by using a crystal oscillator film thickness meter.
(3) Setting the ultraviolet intensity of the ultraviolet radiation system device to 100mW/cm -2 And stopping the deposition process when the deposition thickness reaches 100nm by using a crystal oscillator film thickness meter to obtain a top compact layer.
As shown in FIG. 4, fullerene C 70 The top dense layer has a pronounced absorption peak in the ultraviolet spectral range, which is advantageous in reducing structural degradation of the bottom structural layer by exposure to ultraviolet radiation. As shown in FIG. 5, fullerene C 70 After the top compact layer is decorated on the bottom structural layer, the contact angle of water on the surface of the film is increased from 22 degrees to 89 degrees, which is beneficial to reducing the deterioration of the bottom structural layer caused by the water vapor permeation after the bottom structural layer absorbs moisture.
Example 3
The embodiment provides a composite carbon-based resistor film and a preparation method thereof, wherein the composite carbon-based resistor film consists of a bottom structural layer and a top compact layer which are sequentially arranged from bottom to top; the top compact layer is a fullerene film; the bottom structural layer is comprised of a carbon-based conductive agent and a polymeric binder.
In this embodiment, the preparation process of the bottom structural layer is as follows:
(1) 600mg of epoxy resin was dispersed in 1.5g of a mixed solvent of ethers and ketones, and heated to 60℃to completely dissolve the epoxy resin.
(2) 300mg of Super-P conductive carbon black powder (i.e. amorphous carbon) and 50mg of graphene are dispersed in the mixed solvent of ethers and ketones of the epoxy resin, and the carbon-based resistor paste is prepared after ultrasonic dispersion for 1h at room temperature.
(3) And (3) coating the carbon-based resistor paste on the surface of the substrate by using screen printing equipment, heating to 180 ℃ by using a blast drying oven and keeping for 12 hours, finishing primary drying, and heating to 60 ℃ by using a vacuum drying oven and keeping for 12 hours to finish preparation of the bottom structural layer.
In this example, the top dense layer was prepared as follows:
as shown in FIG. 1, (1) sample the bottom structural layer and fullerene C 60 Is placed in a closed cavity, and the pressure in the closed cavity is reduced to 5 multiplied by 10 by a vacuum system device -4 Pa, and hold for 30min.
(2) Fullerene C using heating system device 60 Heating to 600 ℃ to enable the crystal oscillator film thickness meter to monitor the deposition rate to be about 0.1nm/s.
(3) The ultraviolet intensity of the ultraviolet radiation system device is set to 80mW/cm -2 And stopping the deposition process when the deposition thickness reaches 100nm by using a crystal oscillator film thickness meter to obtain a top compact layer.
As shown in FIG. 6, fullerene C is compared with the bottom structural layer 60 The composite carbon-based resistance film formed by modifying the bottom structural layer with the top compact layer has better stability, and is particularly expressed as 100mW/cm of full spectrum at the temperature of 85 ℃ and the humidity of 85% -2 The rate of change of resistance after 2000h of irradiation was reduced from 132% to 2%.
Example 4
The embodiment provides a composite carbon-based resistor film and a preparation method thereof, wherein the composite carbon-based resistor film consists of a bottom structural layer and a top compact layer which are sequentially arranged from bottom to top; the top compact layer is a fullerene film; the bottom structural layer is comprised of a carbon-based conductive agent and a polymeric binder.
Wherein, the preparation process of the bottom structure layer is as follows:
(1) 600mg of acrylic resin was dispersed in 1.5g of a mixed solvent of ethers and ketones, and heated to 75℃to dissolve the acrylic resin completely.
(2) 300mg of BP2000 superconducting carbon black powder (i.e. amorphous carbon) and 150mg of fullerene are dispersed in the mixed solvent of ethers and ketones of the acrylic resin, and the carbon-based resistor paste is prepared after ultrasonic dispersion for 1h at room temperature.
(3) And (3) coating the carbon-based resistor paste on the surface of the substrate by using screen printing equipment, heating to 175 ℃ by using a blast drying oven and keeping for 12 hours, finishing primary drying, and heating to 60 ℃ by using a vacuum drying oven and keeping for 12 hours to finish preparation of the bottom structural layer.
In addition, the top dense layer of this example was prepared:
as shown in FIG. 1, (1) sample the bottom structural layer and fullerene C 70 Is placed in a closed cavity, and the pressure in the closed cavity is reduced to 5 multiplied by 10 by a vacuum system device -4 Pa, and hold for 30min.
(2) Fullerene C using heating system device 70 Heating to 600 ℃ to enable the crystal oscillator film thickness meter to monitor the deposition rate to be about 0.2nm/s.
(3) Setting the ultraviolet intensity of the ultraviolet radiation system device to 100mW/cm -2 And stopping the deposition process when the deposition thickness reaches 80nm by using a crystal oscillator film thickness meter to obtain a top compact layer.
Fig. 7 and 8 are surface morphologies of the bottom structural layer and the top dense layer, respectively, and it can be found that the top dense layer effectively improves the compactness of the surface of the film, thereby improving the wear resistance of the resistive film. As shown in FIG. 9, fullerene C is compared with the bottom structural layer 70 The composite carbon-based resistance film formed by modifying the bottom structural layer with the top compact layer has better wear resistance, and is particularly expressed as 100mW/cm of full spectrum at the temperature of 85 ℃ and the humidity of 85% -2 The rate of change of resistance after 2000h of irradiation was reduced from 132% to 36%.
The above embodiments are only preferred embodiments of the present invention and are not intended to limit the scope of the present invention, but all changes made by adopting the design principle of the present invention and performing non-creative work on the basis thereof shall fall within the scope of the present invention.
Claims (7)
1. The preparation method of the composite carbon-based resistor film is characterized in that the composite carbon-based resistor film consists of a bottom structural layer and a top compact layer which are sequentially arranged from bottom to top; the top compact layer is a fullerene film; the bottom structural layer is composed of a carbon-based conductive agent and a polymer binder; the fullerene film adopts fullerene C 60 、C 70 、C 76 、C 78 、C 80 、C 84 At least one of (a) and (b);
the mass ratio of the carbon-based conductive agent to the polymer binder is 10-40: 60 to 90;
the preparation method of the composite carbon-based resistor film comprises the following steps:
providing a carbon-based conductive agent and a polymer binder, and uniformly mixing;
adopting printing or knife coating or spraying to prepare the uniformly mixed carbon-based conductive agent and polymer binder into a bottom structural layer; the preparation of the bottom structural layer comprises the following steps:
dispersing the polymer binder in a dissolving agent, heating to 80 ℃, and completely dissolving the polymer binder; adding a carbon-based conductive agent, and performing ultrasonic dispersion for 1h at room temperature to obtain carbon-based resistance slurry for later use;
coating carbon-based resistance slurry on the surface of the epoxy glass fiber laminated board substrate by adopting printing or knife coating or spraying, heating and drying to obtain a bottom structural layer;
preparing a top compact layer on the bottom structural layer by adopting ultraviolet radiation auxiliary gas-phase vacuum thermal evaporation, and obtaining a composite carbon-based resistor film; the preparation of the top dense layer comprises the following steps:
bottom structural layer and fullerene C 60 、C 70 、C 76 、C 78 、C 80 、C 84 Is placed in the closed cavity to reduce the pressure of the closed cavity to 5 multiplied by 10 -4 Pa, holding for 30min;
fullerene C 60 、C 70 、C 76 、C 78 、C 80 、C 84 Heating to 450-700 ℃, adopting ultraviolet radiation, and depositing on the bottom structural layer to obtain a top compact layer with the thickness of 5-1000 nm.
2. The method for preparing a composite carbon-based resistive film according to claim 1, wherein the carbon-based conductive agent is at least one of graphite, graphene, carbon nanotube, carbon fiber, fullerene, and amorphous carbon.
3. The method for preparing a composite carbon-based resistive film according to claim 1, wherein the polymer binder is at least one of phenolic resin, epoxy resin, polyurethane resin, acrylic resin, vinyl acid resin, and nitrile resin.
4. A method of producing a composite carbon-based resistive film according to claim 2 or 3, wherein the thickness of the bottom structural layer is 5 to 500 μm; the thickness of the top compact layer is 5-1000 nm.
5. The method for producing a composite carbon-based resistive film according to claim 1, wherein the ultraviolet radiation has an intensity of 10 to-200 mW/cm -2 。
6. The method for preparing a composite carbon-based resistor film according to claim 1, wherein the deposition rate on the bottom structural layer is 0.01 to-1 nm/s.
7. Use of a composite carbon-based resistive film prepared by the method for preparing a composite carbon-based resistive film according to any one of claims 1 to 6 in a displacement sensor.
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| JP2000249671A (en) * | 1999-02-26 | 2000-09-14 | Sony Corp | Sensor, fullerene-system composite film, and its manufacture |
| JP2001009961A (en) * | 1999-06-25 | 2001-01-16 | Sony Corp | Carbonaceous composite structure and production thereof |
| CN101669177A (en) * | 2007-04-27 | 2010-03-10 | 株式会社可乐丽 | Transparent conductive film and method for producing transparent conductive film |
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| CN110105813A (en) * | 2019-04-15 | 2019-08-09 | 江苏大学 | A kind of carbon-based conductive ink preparation method and the usage |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6793967B1 (en) * | 1999-06-25 | 2004-09-21 | Sony Corporation | Carbonaceous complex structure and manufacturing method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000249671A (en) * | 1999-02-26 | 2000-09-14 | Sony Corp | Sensor, fullerene-system composite film, and its manufacture |
| JP2001009961A (en) * | 1999-06-25 | 2001-01-16 | Sony Corp | Carbonaceous composite structure and production thereof |
| CN101669177A (en) * | 2007-04-27 | 2010-03-10 | 株式会社可乐丽 | Transparent conductive film and method for producing transparent conductive film |
| CN104449010A (en) * | 2014-12-26 | 2015-03-25 | 苏州格瑞丰纳米科技有限公司 | Polymer/graphene anti-static coating, preparation method and application thereof |
| CN110105813A (en) * | 2019-04-15 | 2019-08-09 | 江苏大学 | A kind of carbon-based conductive ink preparation method and the usage |
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