CN110551435A - preparation method of composite carbon-based electric heating coating - Google Patents
preparation method of composite carbon-based electric heating coating Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 64
- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000005485 electric heating Methods 0.000 title claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 239000000945 filler Substances 0.000 claims abstract description 38
- 239000002133 porous carbon nanofiber Substances 0.000 claims abstract description 33
- 241000237536 Mytilus edulis Species 0.000 claims abstract description 26
- 235000020638 mussel Nutrition 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000010355 oscillation Effects 0.000 claims abstract description 14
- 238000010008 shearing Methods 0.000 claims abstract description 13
- 102000030523 Catechol oxidase Human genes 0.000 claims abstract description 11
- 108010031396 Catechol oxidase Proteins 0.000 claims abstract description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 10
- 239000004246 zinc acetate Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 239000002121 nanofiber Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 17
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 16
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000010041 electrostatic spinning Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 3
- 239000003973 paint Substances 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical group OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 abstract description 5
- 229910052709 silver Inorganic materials 0.000 abstract description 5
- 239000004332 silver Substances 0.000 abstract description 5
- 230000009920 chelation Effects 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 23
- 238000007598 dipping method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012799 electrically-conductive coating Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of paint preparation, and particularly relates to a preparation method of a composite carbon-based electric heating paint. The invention takes polyacrylonitrile and zinc acetate as raw materials to obtain porous carbon nanofiber, then the porous carbon nanofiber is mixed with mussel mucin liquid and added with catechol oxidase for ultrasonic oscillation to obtain reaction filter residue, then mixing the reaction filter residue and silver nitrate solution, sintering at high temperature to obtain self-made composite carbon-based filler, finally blending and shearing the self-made composite carbon-based filler, resin and other additives to obtain the composite carbon-based electrothermal coating, wherein oxidized dopa groups and unoxidized dopa groups are crosslinked to form a high-molecular reticular polymer which is adsorbed on the inner pores and the surface of the porous carbon nanofiber and has metal ion chelation, a layer of carbon nano conduction band network is generated between the interface of the metal silver and the porous carbon nanofiber, so that the conductivity of the composite material is increased.
Description
Technical Field
the invention belongs to the technical field of paint preparation, and particularly relates to a preparation method of a composite carbon-based electric heating paint.
Background
In recent years, the traditional electric heating materials such as metal tungsten, molybdenum, nickel and alloys thereof are gradually replaced by novel electric heating materials due to the defects of large material consumption, short service life, difficult processing and forming, unstable working conditions and the like. The electrothermal film is used as a product of a heating element and is widely applied to various fields such as industry, agriculture and the like.
The electrothermal film is also called as metal oxide electrothermal film. The conductive coating is printed on the film and is prepared by the aid of materials such as metal current-carrying strips and conductive silver paste. It has the features of high melting point, high hardness, low resistance, high heat efficiency, high chemical stability, etc. The core heating element of the electrothermal film is electrothermal paint, and the quality of the electrothermal film directly determines the product strength of the electrothermal film.
The electrothermal coating is one kind of functional coating, and is one kind of new functional coating with excellent electrothermal characteristic developed based on electrically conductive coating. It can be coated on the surface or any surface of the object to be heated like paint to heat, and has extremely high thermal efficiency because it can be directly coated on the surface of the substrate. The electrothermal coating is nontoxic and harmless, safe and durable, has excellent performance, has the advantages of long service life, power saving, convenience, safety, reliability and the like compared with an electric heater, and has wide application prospects in various aspects of production and life, such as building heating, industrial oven drying, petrochemical pipeline heat preservation and the like. With the continuous development of the scientific and technological industry, the performance requirements for functional coatings are continuously improved.
The electrothermal paint widely used in the market at present is a functional paint which takes carbon materials such as carbon black, graphite and the like as conductive agents, uniformly disperses the conductive agents in an organic carrier, simultaneously coats the conductive agents on insulating base materials such as PET, epoxy glass fiber boards, ceramic panels and the like in a coating, silk-screen printing, gravure and the like mode, takes a conductive current carrying strip as two end electrodes, and applies voltage to the two ends of the electrode, thereby stably generating heat. The electrothermal filler endows the electrothermal paint with electrothermal performance, and the electrothermal filler mainly comprises a metal series, a carbon series and the like. The metal system has good conductivity, but is easy to oxidize, which can seriously affect the conductivity of the coating and further affect the heating effect of the coating, wherein the gold powder and the silver powder in the metal powder can not be oxidized but have high cost, thus seriously limiting the practical application of the coating, and in addition, the coating has the problem of sedimentation due to the high density of the metal powder; the carbon series filler has the advantages of light weight, no toxicity, no harm, difficult oxidation, low price and the like, is widely applied to electric heating coatings at home and abroad, but the electric heating performance of the carbon series filler is still different from metals, and the resistivity of the carbon series filler is larger than that of the metals such as silver, copper, nickel, aluminum and the like, so that the electric heating coatings of the carbon series filler are slow in temperature rise and low in temperature, and are difficult to be widely applied. If the resistance value is reduced by increasing the content of the conductive filler, the adhesion of the coating is reduced, and the service life of the coating is affected. Several electrothermal paint patents are disclosed in the market at present, which mainly adopt carbon powder and graphite as fillers, and have the problems that the resistance of the electrothermal paint is more than dozens of ohms, if the content of the conductive fillers is further increased to reduce the resistance, the adhesive force of the coating is deteriorated, the heating efficiency is relatively low in practical use, higher voltage (higher than 36 volt-ampere full voltage) is required, and the practical application is not facilitated.
most of electric heating coatings in the prior art have the defects of low surface heating temperature, low heating rate, uneven heating temperature, low heating efficiency, low maximum temperature of less than 200 ℃, poor heat resistance and aging resistance, long service life, easy power decline, short service life and the like, and seriously restrict the rapid development and the application of the electric heating coatings in many fields.
Therefore, it is an urgent problem in the art to provide an electrothermal paint capable of solving the above problems.
Disclosure of Invention
The invention mainly solves the technical problem and provides a preparation method of a composite carbon-based electric heating coating, aiming at the defects that the carbon-based filler in the existing electric heating coating has the advantages of light weight, no toxicity, no harm, difficult oxidation, low price and the like, but the carbon-based electric heating coating still has difference with metal and larger resistivity, so that the carbon-based electric heating coating is slow in temperature rise and low in temperature and is difficult to widely apply.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the specific preparation steps of the composite carbon-based electric heating coating are as follows:
Weighing self-made composite carbon-based filler, epoxy resin, dibutyl phthalate, stearic acid and cyclohexanone, mixing, putting into a high-speed shearing emulsifying machine, carrying out high-speed shearing dispersion treatment for 10-20 min at a rotating speed of 2000-3000 r/min, and discharging to obtain the composite carbon-based electric heating coating;
The preparation method of the self-made composite carbon-based filler comprises the following steps:
(1) Mixing mussel mucin with deionized water to obtain mussel mucin liquid, mixing porous carbon nanofibers with the mussel mucin liquid, pouring the mixture into a beaker, and adjusting the pH to 7.5-8.0 by using a sodium hydroxide solution with the concentration of 0.1mol/L to obtain a mixed solution;
(2) Mixing the obtained mixed solution with catechol oxidase, putting the mixture into an ultrasonic oscillation instrument, carrying out ultrasonic oscillation reaction, and filtering and separating after the reaction is finished to obtain reaction filter residue;
(3) Mixing the reaction filter residue with a silver nitrate solution with the concentration of 1mol/L, shaking and soaking for 3-5 h by using a shaking table, filtering and separating after soaking to obtain a soaked filter cake, putting the soaked filter cake into a sintering furnace, sintering under the protection of nitrogen, and obtaining the self-made composite carbon-based filler after sintering;
The preparation steps of the porous carbon nanofiber are as follows:
(1) Weighing polyacrylonitrile and zinc acetate, mixing to obtain a mixture, mixing the mixture and N, N-dimethylformamide, putting the mixture into a beaker, transferring the beaker into a water bath, and stirring for 3-4 hours at the temperature of 60-70 ℃ to obtain yellow viscous liquid;
(2) Loading the yellow viscous liquid into electrostatic spinning equipment, applying a voltage of 10-11 kV on a needle head, taking a grounded stainless steel plate as a negative electrode receiving screen which is 15cm away from the needle head, controlling the flow of an injection pump to be 0.3mL/h, and spraying the yellow viscous liquid into filaments to obtain composite nano fibers;
(3) and (2) placing the obtained composite nanofiber into a resistance furnace, carrying out pre-oxidation treatment in air, carrying out heat preservation carbonization in an argon atmosphere after the pre-oxidation treatment is finished, sequentially placing carbonized products into a nitric acid solution with the concentration of 3mol/L and deionized water to respectively soak for 1-2 h after the carbonization is finished, and drying after the soaking is finished to obtain the porous carbon nanofiber.
in the specific preparation steps of the composite carbon-based electrothermal coating, by weight, 40-50 parts of self-made composite carbon-based filler, 70-80 parts of epoxy resin, 5-10 parts of dibutyl phthalate, 5-10 parts of stearic acid and 50-100 parts of cyclohexanone.
in the step (1) of preparing the self-made composite carbon-based filler, the mass ratio of the mussel mucin to the deionized water is 1:5, and the mass ratio of the porous carbon nanofiber to the mussel mucin liquid is 1: 10.
In the step (2) of preparing the self-made composite carbon-based filler, the mass ratio of the mixed liquid to the catechol oxidase is 50:1, the frequency of the ultrasonic oscillation reaction is 25-30 kHz, and the time of the ultrasonic oscillation reaction is 3-4 h.
In the step (3) of preparing the self-made composite carbon-based filler, the mass ratio of the reaction filter residue to the silver nitrate solution with the concentration of 1mol/L is 1:10, the sintering temperature is 400-500 ℃, and the sintering time is 4-6 hours.
In the preparation step (1) of the porous carbon nanofiber, the mass ratio of polyacrylonitrile to zinc acetate is 3:2, and the mass ratio of the mixture to N, N-dimethylformamide is 1: 3.
In the step (3) of preparing the porous carbon nanofiber, the temperature of pre-oxidation treatment is 200-300 ℃, the time of pre-oxidation treatment is 1-2 h, the temperature of heat preservation carbonization is 800-900 ℃, and the time of heat preservation carbonization is 2-3 h.
The beneficial technical effects of the invention are as follows:
(1) The invention firstly uses polyacrylonitrile and zinc acetate as raw materials, and carries out carbonization after electrostatic spinning and removes zinc oxide by nitric acid and water soaking, thereby obtaining porous carbon nanofiber, then mixes the porous carbon nanofiber and mussel mucin liquid, adjusts the mixture to be alkaline, and adds catechol oxidase to carry out ultrasonic oscillation reaction to obtain reaction filter residue, then mixes and soaks the reaction filter residue and silver nitrate solution, and carries out high-temperature sintering to obtain self-made composite carbon-based filler, and finally blends, shears and disperses the self-made composite carbon-based filler, resin and other additives to obtain the composite carbon-based electrothermal coating. Under the action of alkalinity and catechol oxidase, phenolic hydroxyl in mussel mucin dopa group is oxidized into quinone, the oxidized dopa group and unoxidized dopa group are crosslinked to form a high molecular network polymer which is adsorbed on the inner pores and the surface of the porous carbon nanofiber, the formed high molecular network polymer has metal ion chelation, the porous carbon nanofiber treated by mussel mucin liquid is mixed with silver nitrate solution, a large amount of silver ions are adsorbed and fixed on the surface and the pores of the carbon nanofiber by utilizing the metal ion chelation of the high molecular network polymer, and then the carbon nanofiber is calcined at high temperature to prepare a composite carbon-based conductive medium with stable property, a layer of carbon nano conduction band network is generated between the interface of metal silver and the porous carbon nanofiber due to the catalytic action of the metal silver, and the structure of the nano carbon is in a graphite structure, the self-made composite carbon-based filler used by the invention is fibrous and not powdery, and can be arranged in a disordered manner when being dispersed in the coating to form a physical conductive network, so that the electrical resistivity of the electrothermal coating can be further reduced, the electrothermal coating has high electrical heating performance, low electrical resistivity, quick temperature rise and high temperature, and has wide application prospect.
Detailed Description
Weighing polyacrylonitrile and zinc acetate according to a mass ratio of 3:2, mixing to obtain a mixture, mixing the mixture and N, N-dimethylformamide according to a mass ratio of 1:3, putting the mixture into a beaker, transferring the beaker into a water bath kettle, and stirring for 3-4 hours at 60-70 ℃ to obtain yellow viscous liquid; loading the yellow viscous liquid into electrostatic spinning equipment, applying a voltage of 10-11 kV on a needle head, taking a grounded stainless steel plate as a negative electrode receiving screen which is 15cm away from the needle head, controlling the flow of an injection pump to be 0.3mL/h, and spraying the yellow viscous liquid into filaments to obtain composite nano fibers; putting the obtained composite nanofiber into a resistance furnace, heating in air to 200-300 ℃, carrying out pre-oxidation treatment for 1-2 h, heating in an argon atmosphere to 800-900 ℃ after the pre-oxidation treatment is finished, carrying out heat preservation carbonization for 2-3 h, sequentially putting carbonized products into 3mol/L nitric acid solution and deionized water to be respectively soaked for 1-2 h after the carbonization is finished, and drying after the soaking is finished to obtain the porous carbon nanofiber; mixing mussel mucin and deionized water according to the mass ratio of 1:5 to obtain mussel mucin liquid, mixing the obtained porous carbon nanofiber and the mussel mucin liquid according to the mass ratio of 1:10, pouring the mixture into a beaker, and adjusting the pH to 7.5-8.0 by using a sodium hydroxide solution with the concentration of 0.1mol/L to obtain a mixed solution; mixing the obtained mixed solution and catechol oxidase according to the mass ratio of 50:1, putting the mixture into an ultrasonic oscillator, carrying out ultrasonic oscillation reaction for 3-4 h at the frequency of 25-30 kHz, and filtering and separating after the reaction is finished to obtain reaction filter residue; mixing the reaction filter residue with a silver nitrate solution with the concentration of 1mol/L according to the mass ratio of 1:10, shaking and dipping for 3-5 h by using a shaking table, filtering and separating after dipping to obtain a dipped filter cake, then putting the dipped filter cake into a sintering furnace, heating to 400-500 ℃ under the protection of nitrogen, sintering for 4-6 h, and obtaining the self-made composite carbon-based filler after sintering; weighing 40-50 parts by weight of self-made composite carbon-based filler, 70-80 parts by weight of epoxy resin, 5-10 parts by weight of dibutyl phthalate, 5-10 parts by weight of stearic acid and 50-100 parts by weight of cyclohexanone, mixing, putting into a high-speed shearing emulsifying machine, carrying out high-speed shearing dispersion treatment at a rotating speed of 2000-3000 r/min for 10-20 min, and discharging to obtain the composite carbon-based electrothermal coating.
example 1
preparing yellow viscous liquid:
weighing polyacrylonitrile and zinc acetate according to a mass ratio of 3:2, mixing to obtain a mixture, mixing the mixture and N, N-dimethylformamide according to a mass ratio of 1:3, putting the mixture into a beaker, transferring the beaker into a water bath kettle, and stirring for 3 hours at 60 ℃ to obtain yellow viscous liquid.
Preparing the composite nanofiber:
And (3) putting the yellow viscous liquid into electrostatic spinning equipment, applying a voltage of 10kV on a needle head, taking a grounded stainless steel plate as a negative electrode receiving screen, keeping the distance from the needle head by 15cm, controlling the flow of an injection pump to be 0.3mL/h, and spraying the yellow viscous liquid into filaments to obtain the composite nanofiber.
preparing porous carbon nanofiber:
and (2) putting the obtained composite nanofiber into a resistance furnace, heating the composite nanofiber to 200 ℃ in air, carrying out pre-oxidation treatment for 1h, heating the composite nanofiber to 800 ℃ in an argon atmosphere after the pre-oxidation treatment is finished, carrying out heat preservation carbonization for 2h, sequentially putting carbonized products into 3mol/L nitric acid solution and deionized water to respectively soak for 1h after carbonization is finished, and drying the carbonized products after soaking is finished to obtain the porous carbon nanofiber.
Preparing a mixed solution:
Mixing mussel mucin and deionized water according to the mass ratio of 1:5 to obtain mussel mucin liquid, mixing the obtained porous carbon nanofiber and the mussel mucin liquid according to the mass ratio of 1:10, pouring the mixture into a beaker, and adjusting the pH to 7.5 by using a sodium hydroxide solution with the concentration of 0.1mol/L to obtain a mixed solution.
preparation of reaction filter residue:
mixing the obtained mixed solution and catechol oxidase according to the mass ratio of 50:1, putting into an ultrasonic oscillator, carrying out ultrasonic oscillation reaction for 3h at the frequency of 25kHz, and filtering and separating after the reaction is finished to obtain reaction filter residue.
Preparing a self-made composite carbon-based filler:
mixing the reaction filter residue and a silver nitrate solution with the concentration of 1mol/L according to the mass ratio of 1:10, shaking and dipping for 3 hours by using a shaking table, filtering and separating after dipping to obtain a dipping filter cake, then putting the dipping filter cake into a sintering furnace, heating to 400 ℃ under the protection of nitrogen, sintering for 4 hours, and obtaining the self-made composite carbon-based filler after sintering.
Preparing the composite carbon-based electric heating coating:
Weighing 40 parts by weight of self-made composite carbon-based filler, 70 parts by weight of epoxy resin, 5 parts by weight of dibutyl phthalate, 5 parts by weight of stearic acid and 50 parts by weight of cyclohexanone, mixing, putting into a high-speed shearing emulsifying machine, carrying out high-speed shearing dispersion treatment for 10min at a rotating speed of 2000r/min, and discharging to obtain the composite carbon-based electric heating coating.
Example 2
Preparing yellow viscous liquid:
Weighing polyacrylonitrile and zinc acetate according to a mass ratio of 3:2, mixing to obtain a mixture, mixing the mixture and N, N-dimethylformamide according to a mass ratio of 1:3, putting the mixture into a beaker, transferring the beaker into a water bath kettle, and stirring for 3 hours at 65 ℃ to obtain yellow viscous liquid.
preparing the composite nanofiber:
And (3) putting the yellow viscous liquid into electrostatic spinning equipment, applying a voltage of 10kV on a needle head, taking a grounded stainless steel plate as a negative electrode receiving screen, keeping the distance from the needle head by 15cm, controlling the flow of an injection pump to be 0.3mL/h, and spraying the yellow viscous liquid into filaments to obtain the composite nanofiber.
preparing porous carbon nanofiber:
And (2) putting the obtained composite nanofiber into a resistance furnace, heating the composite nanofiber in air to 250 ℃, carrying out preoxidation treatment for 2 hours, heating the composite nanofiber to 850 ℃ in an argon atmosphere after the preoxidation treatment is finished, carrying out heat preservation carbonization for 3 hours, sequentially putting carbonized products into 3mol/L nitric acid solution and deionized water to respectively soak for 1 hour after the carbonization is finished, and drying the carbonized products after the soaking is finished to obtain the porous carbon nanofiber.
Preparing a mixed solution:
Mixing mussel mucin and deionized water according to the mass ratio of 1:5 to obtain mussel mucin liquid, mixing the obtained porous carbon nanofiber and the mussel mucin liquid according to the mass ratio of 1:10, pouring the mixture into a beaker, and adjusting the pH to 7.7 by using a sodium hydroxide solution with the concentration of 0.1mol/L to obtain a mixed solution.
preparation of reaction filter residue:
Mixing the obtained mixed solution and catechol oxidase according to the mass ratio of 50:1, putting into an ultrasonic oscillator, carrying out ultrasonic oscillation reaction for 3h at the frequency of 27kHz, and filtering and separating after the reaction is finished to obtain reaction filter residue.
Preparing a self-made composite carbon-based filler:
Mixing the reaction filter residue and a silver nitrate solution with the concentration of 1mol/L according to the mass ratio of 1:10, shaking and dipping for 4 hours by using a shaking table, filtering and separating after dipping to obtain a dipping filter cake, then putting the dipping filter cake into a sintering furnace, heating to 450 ℃ under the protection of nitrogen, sintering for 5 hours, and obtaining the self-made composite carbon-based filler after sintering.
Preparing the composite carbon-based electric heating coating:
weighing 45 parts by weight of self-made composite carbon-based filler, 75 parts by weight of epoxy resin, 7 parts by weight of dibutyl phthalate, 7 parts by weight of stearic acid and 70 parts by weight of cyclohexanone, mixing, putting into a high-speed shearing emulsifying machine, carrying out high-speed shearing dispersion treatment for 15min at the rotating speed of 2500r/min, and discharging to obtain the composite carbon-based electric heating coating.
Example 3
preparing yellow viscous liquid:
Weighing polyacrylonitrile and zinc acetate according to a mass ratio of 3:2, mixing to obtain a mixture, mixing the mixture and N, N-dimethylformamide according to a mass ratio of 1:3, putting the mixture into a beaker, transferring the beaker into a water bath kettle, and stirring for 4 hours at 70 ℃ to obtain yellow viscous liquid.
preparing the composite nanofiber:
and (3) putting the yellow viscous liquid into electrostatic spinning equipment, applying 11kV voltage on a needle head, taking a grounded stainless steel plate as a negative electrode receiving screen, keeping the distance from the needle head by 15cm, controlling the flow of an injection pump to be 0.3mL/h, and spraying the yellow viscous liquid into filaments to obtain the composite nanofiber.
preparing porous carbon nanofiber:
and (2) putting the obtained composite nanofiber into a resistance furnace, heating the composite nanofiber to 300 ℃ in air, carrying out pre-oxidation treatment for 2h, heating the composite nanofiber to 900 ℃ in an argon atmosphere after the pre-oxidation treatment is finished, carrying out heat preservation carbonization for 3h, sequentially putting carbonized products into 3mol/L nitric acid solution and deionized water to respectively soak for 2h after the carbonization is finished, and drying the carbonized products after the soaking is finished to obtain the porous carbon nanofiber.
Preparing a mixed solution:
Mixing mussel mucin and deionized water according to the mass ratio of 1:5 to obtain mussel mucin liquid, mixing the obtained porous carbon nanofiber and the mussel mucin liquid according to the mass ratio of 1:10, pouring the mixture into a beaker, and adjusting the pH to 8.0 by using a sodium hydroxide solution with the concentration of 0.1mol/L to obtain a mixed solution.
Preparation of reaction filter residue:
Mixing the obtained mixed solution and catechol oxidase according to the mass ratio of 50:1, putting into an ultrasonic oscillator, carrying out ultrasonic oscillation reaction for 4 hours at the frequency of 30kHz, and filtering and separating after the reaction is finished to obtain reaction filter residue.
Preparing a self-made composite carbon-based filler:
Mixing the reaction filter residue and a silver nitrate solution with the concentration of 1mol/L according to the mass ratio of 1:10, shaking and soaking for 5 hours by using a shaking table, filtering and separating after soaking to obtain a soaked filter cake, then putting the soaked filter cake into a sintering furnace, heating to 500 ℃ under the protection of nitrogen, sintering for 6 hours, and obtaining the self-made composite carbon-based filler after sintering.
Preparing the composite carbon-based electric heating coating:
Weighing 50 parts by weight of self-made composite carbon-based filler, 80 parts by weight of epoxy resin, 10 parts by weight of dibutyl phthalate, 10 parts by weight of stearic acid and 100 parts by weight of cyclohexanone, mixing, putting into a high-speed shearing emulsifying machine, carrying out high-speed shearing dispersion treatment at a rotating speed of 3000r/min for 20min, and discharging to obtain the composite carbon-based electric heating coating.
Comparative example 1: essentially the same procedure as in example 1 was followed, except that the porous carbon nanofibers were not incorporated.
Comparative example 2: the procedure was essentially the same as in example 2, except that no reaction residue was added.
Comparative example 3: an electrothermal coating produced by a certain company in Chengdu city.
The composite carbon-based electric heating coating prepared by the invention and the electric heating coating in the comparative example are detected, and the detection results are shown in table 1:
Adhesion test
The determination is carried out with reference to the standard GB/T9286 test for marking and marking paint films.
Resistivity testing
The surface resistivity was measured by using a surface resistivity tester.
TABLE 1 measurement results of Properties
| Test items | Example 1 | example 2 | Example 3 | comparative example 1 | comparative example 2 | Comparative example 3 |
| Storage stability (50 ℃, 30 d) | No change in appearance and performance | no change in appearance and performance | No change in appearance and performance | No change in appearance and performance | A small amount of delamination occurred | A large number of layers occurred |
| Adhesion (grade) | level 1 | Level 1 | Level 0 | Stage 2 | Level 1 | Stage 2 |
| volume resistivity (omega cm) | 0.9 | 0.7 | 0.6 | 1.1 | 1.0 | 1.3 |
| energization time (min) | 30 | 26 | 24 | 36 | 33 | 42 |
| Surface Final constant temperature (. degree. C.) | 186 | 193 | 200 | 143 | 167 | 174 |
The data in table 1 show that the composite carbon-based electrothermal coating prepared by the invention has the advantages of strong adhesive force, small resistivity, good storage stability and the like, can ensure that the long-term use temperature is between 100 and 220 ℃, has uniform heating temperature, does not generate power recession after long-term use, has simple preparation process, no pollution and low cost, is suitable for large-scale industrial production, and has wide application prospect.
Claims (7)
1. A preparation method of a composite carbon-based electric heating coating is characterized by comprising the following specific preparation steps:
Weighing self-made composite carbon-based filler, epoxy resin, dibutyl phthalate, stearic acid and cyclohexanone, mixing, putting into a high-speed shearing emulsifying machine, carrying out high-speed shearing dispersion treatment for 10-20 min at a rotating speed of 2000-3000 r/min, and discharging to obtain the composite carbon-based electric heating coating;
The preparation steps of the self-made composite carbon-based filler are as follows:
(1) mixing mussel mucin with deionized water to obtain mussel mucin liquid, mixing porous carbon nanofibers with the mussel mucin liquid, pouring the mixture into a beaker, and adjusting the pH to 7.5-8.0 by using a sodium hydroxide solution with the concentration of 0.1mol/L to obtain a mixed solution;
(2) Mixing the obtained mixed solution with catechol oxidase, putting the mixture into an ultrasonic oscillation instrument, carrying out ultrasonic oscillation reaction, and filtering and separating after the reaction is finished to obtain reaction filter residue;
(3) mixing the reaction filter residue with a silver nitrate solution with the concentration of 1mol/L, shaking and soaking for 3-5 h by using a shaking table, filtering and separating after soaking to obtain a soaked filter cake, putting the soaked filter cake into a sintering furnace, sintering under the protection of nitrogen, and obtaining the self-made composite carbon-based filler after sintering;
The preparation steps of the porous carbon nanofiber are as follows:
(1) Weighing polyacrylonitrile and zinc acetate, mixing to obtain a mixture, mixing the mixture and N, N-dimethylformamide, putting the mixture into a beaker, transferring the beaker into a water bath, and stirring for 3-4 hours at the temperature of 60-70 ℃ to obtain yellow viscous liquid;
(2) loading the yellow viscous liquid into electrostatic spinning equipment, applying a voltage of 10-11 kV on a needle head, taking a grounded stainless steel plate as a negative electrode receiving screen which is 15cm away from the needle head, controlling the flow of an injection pump to be 0.3mL/h, and spraying the yellow viscous liquid into filaments to obtain composite nano fibers;
(3) And (2) placing the obtained composite nanofiber into a resistance furnace, carrying out pre-oxidation treatment in air, carrying out heat preservation carbonization in an argon atmosphere after the pre-oxidation treatment is finished, sequentially placing carbonized products into a nitric acid solution with the concentration of 3mol/L and deionized water to respectively soak for 1-2 h after the carbonization is finished, and drying after the soaking is finished to obtain the porous carbon nanofiber.
2. the preparation method of the composite carbon-based electrothermal coating according to claim 1, characterized in that: in the specific preparation steps of the composite carbon-based electrothermal coating, by weight, 40-50 parts of a self-made composite carbon-based filler, 70-80 parts of epoxy resin, 5-10 parts of dibutyl phthalate, 5-10 parts of stearic acid and 50-100 parts of cyclohexanone.
3. The preparation method of the composite carbon-based electrothermal coating according to claim 1, characterized in that: in the step (1) of preparing the self-made composite carbon-based filler, the mass ratio of the mussel mucin to the deionized water is 1:5, and the mass ratio of the porous carbon nanofiber to the mussel mucin liquid is 1: 10.
4. The preparation method of the composite carbon-based electrothermal coating according to claim 1, characterized in that: in the step (2) of preparing the self-made composite carbon-based filler, the mass ratio of the mixed solution to the catechol oxidase is 50:1, the frequency of the ultrasonic oscillation reaction is 25-30 kHz, and the time of the ultrasonic oscillation reaction is 3-4 h.
5. the preparation method of the composite carbon-based electrothermal coating according to claim 1, characterized in that: in the step (3) of preparing the self-made composite carbon-based filler, the mass ratio of reaction filter residues to a silver nitrate solution with the concentration of 1mol/L is 1:10, the sintering temperature is 400-500 ℃, and the sintering time is 4-6 hours.
6. The preparation method of the composite carbon-based electrothermal coating according to claim 1, characterized in that: in the preparation step (1) of the porous carbon nanofiber, the mass ratio of polyacrylonitrile to zinc acetate is 3:2, and the mass ratio of the mixture to N, N-dimethylformamide is 1: 3.
7. the preparation method of the composite carbon-based electrothermal coating according to claim 1, characterized in that: in the preparation step (3) of the porous carbon nanofiber, the temperature of pre-oxidation treatment is 200-300 ℃, the time of pre-oxidation treatment is 1-2 h, the temperature of heat preservation carbonization is 800-900 ℃, and the time of heat preservation carbonization is 2-3 h.
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