CN113621273A - Self-temperature-limiting conductive ink, preparation method and heating ceramic - Google Patents
Self-temperature-limiting conductive ink, preparation method and heating ceramic Download PDFInfo
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- CN113621273A CN113621273A CN202111190161.8A CN202111190161A CN113621273A CN 113621273 A CN113621273 A CN 113621273A CN 202111190161 A CN202111190161 A CN 202111190161A CN 113621273 A CN113621273 A CN 113621273A
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- 238000010438 heat treatment Methods 0.000 title abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 90
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- 238000011049 filling Methods 0.000 claims abstract description 23
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- 229910052681 coesite Inorganic materials 0.000 claims abstract description 19
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- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
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- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
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- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 claims description 6
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- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000670 limiting effect Effects 0.000 claims description 4
- 229940116411 terpineol Drugs 0.000 claims description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims 2
- 239000011231 conductive filler Substances 0.000 claims 2
- 238000013021 overheating Methods 0.000 abstract description 9
- 239000000976 ink Substances 0.000 description 59
- 230000000052 comparative effect Effects 0.000 description 20
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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Images
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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
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/141—Conductive ceramics, e.g. metal oxides, metal carbides, barium titanate, ferrites, zirconia, vitrous compounds
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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)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to the technical field of conductive ink, and discloses self-temperature-limiting conductive ink, a preparation method and heating ceramic, which are prepared from the following raw materials in percentage by mass: 18-45% of carbon-based conductive filling material, 6-10% of self-temperature-limiting material, 20-48% of resin bonding material, 3-6% of additive and 25-45% of solvent; the self-temperature-limiting material is prepared from the following raw materials in percentage by mass: BaTiO 23 41%～65%、SrTiO3 30％～50%、Cr2O3 5％～9%、La2O3 3％～7%、CaCO3 0.5％～1%、SiO2 0.4％～1%、Al2O30.1 to 0.5 percent. The self-temperature-limiting material is added into the formula of the conductive ink, so that the conductive ink has a self-temperature-limiting function, the circuit damage and the thermal attenuation caused by circuit overheating are prevented, the resistance value can be rapidly increased under a high-temperature condition, the self-temperature-limiting conductive ink is effectively stopped to generate heat in a temperature range, the heating temperature is not higher than 120 ℃, the internal resin bonding material is not melted, the influence on the internal structure of the heating ceramic tile is small, and the conductive ink can be used for a long time.
Description
Technical Field
The invention relates to the technical field of conductive ink, in particular to self-temperature-limiting conductive ink, a preparation method and heating ceramic.
Background
The heating film is one of heating materials commonly used for heating ceramics, contains a layer of graphene film resistor, and is prepared by printing graphene resistor slurry on a PET film. When the ceramic that generates heat when the use in the foreign matter like steam immerses heating film inside, because steam can lead to partial metal component to produce the corrosion, the damage can appear in the component of corrosion, when partial piece drops and covers on heating film, heating film will produce local high temperature in this region, general film resistor's accumulated heat temperature can not exceed substrate softening point temperature (below 130 ℃), otherwise overheated can lead to heating film (PET film) to soften and produce the dilatational strain, can occupy the original position of graphite alkene resistance after partial PET material shifts, and then lead to the electrically conductive channel quantity in the graphite alkene film to reduce, the ceramic that generates heat produces irreversible heating power decay, use effect and life have been reduced.
And the temperature control mode of the existing heating ceramic is mainly realized through a temperature control system, wherein temperature point measurement is carried out on each position of the electrothermal film by a temperature control probe of the temperature controller so as to prevent overheating. In the actual use process, the number of the temperature control probes is limited, a part of heat accumulation areas are not detectable by the temperature control probes, the whole temperature control effect cannot be achieved, and the thin film resistor is easy to soften due to local overheating to cause circuit damage, so that the temperature limit of the thin film resistor is necessarily expanded from point to surface, the temperature of the heating ceramic is comprehensively limited, and overheating is prevented.
Disclosure of Invention
The invention mainly aims to provide a self-temperature-limiting conductive ink and a preparation method thereof, and aims to solve the technical problems that the heating power is easy to attenuate due to local overheating of the existing heating ceramic, and the overall temperature control cannot be realized.
In order to achieve the purpose, the invention provides a self-temperature-limiting conductive ink which is prepared from the following raw materials in percentage by mass: 18-45% of carbon-based conductive filling material, 6-10% of self-temperature-limiting material, 20-48% of resin bonding material, 3-6% of additive and 25-45% of solvent;
the self-temperature-limiting material is prepared from the following raw materials in percentage by mass: BaTiO 23 41%～65%、SrTiO327％～50%、Cr2O3 5％～9%、La2O3 3％～7%、CaCO3 0.5％～1%、SiO2 0.4％～1%、Al2O30.1％～0.5%；
Wherein, BaTiO3、SrTiO3、Cr2O3And La2O3The mass ratio of (1): (0.45-1): (0.1-0.23): (0.05-0.15).
The self-temperature-limiting conductive ink mainly comprises a carbon-based conductive filling material, a resin bonding material and a solvent, wherein the carbon-based conductive filling material is heated immediately after being electrified, heat is continuously generated at the bottom of a ceramic tile, the resin component is mainly used for connecting and fixing the carbon-based conductive filling material and the ceramic tile, and the solvent is convenient for uniformly dispersing all components, so that the self-temperature-limiting conductive ink has the best use effect. The self-temperature-limiting conductive ink in the scheme adds a special self-temperature-limiting material, when the self-temperature-limiting material reaches a Curie temperature point, the volume can be expanded properly, a conductive network formed by conductive particles can lead to the increase of microscopic distance among the particles due to the expansion of the self-temperature-limiting material, thereby the resistivity of the material is greatly increased, the film resistance value formed by curing the conductive ink can be rapidly increased, the output power is greatly reduced, even approaching zero, and therefore the purpose of controlling the temperature of the whole heating module to prevent overheating is achieved. The addition of the additive can improve the performance of the conductive ink to adapt to the use of different scenes.
The self-temperature-limiting material mainly comprises BaTiO3、PbTiO3、Cr、Ni、CaCO3、SiO2And Al2O3The scheme is realized by limiting BaTiO3、SrTiO3、Cr2O3And La2O3The mass ratio of the components is used for controlling the resistivity, so that the temperature control effect of the heating ceramic is controlled, other raw materials can be freely added within a limited dosage range, and the influence on the temperature control effect of the heating ceramic is relatively small.
Preferably, the carbon-based conductive filling material is at least one of graphene, nano carbon powder and carbon nanotubes. The graphene, the carbon nano-powder and the carbon nano-tube are all materials with excellent conductivity, and the carbon-based conductive filling material can be selected from any one, two or three of the above three materials. Wherein the particle size (D50) of the graphene is 7-12 μm, the bulk density is 0.01-0.02 g/ml, and the powder sheet resistance is 1-9 m omega cm; the average particle diameter of the nano carbon powder is 20nm, and the volume density is 0.2g/cm3Specific surface area 35m2(ii)/g; the carbon nanotube has a diameter of 10-20 nm, a length of 10-30 μm, and a specific surface area of more than 200m2(ii) a bulk density of 0.25 to 0.27g/ml, an electrical conductivity>150s/cm。
Preferably, the carbon-based conductive filling material is prepared from the following raw materials in percentage by mass: 33% of graphene, 28% of nano carbon powder and 39% of carbon nano tubes. When the self-temperature-limiting conductive ink is prepared from the three raw materials, a good heating effect and a good temperature control effect can be ensured.
Preferably, the resin bonding material is resin with a melting point higher than 320 ℃, and the particle size of the resin bonding material is 3-10 μm.
Because the self-temperature-limiting conductive ink needs to be printed on a ceramic tile, silver paste is printed, then the self-temperature-limiting conductive ink needs to be dried and solidified at the temperature of more than 100-120 ℃ for 30min, so that the normal use of heating ceramic is ensured, the traditional epoxy resin can be softened at the temperature to cause the infirm adhesion with a ceramic tile substrate, therefore, the resin with higher melting point (the melting point is more than 320 ℃) needs to be selected to realize the firm connection of the self-temperature-limiting conductive ink and the ceramic tile substrate, the resin bonding material can specifically use polytetrafluoroethylene resin or polyimide resin, and the good screen printing effect of the self-temperature-limiting conductive ink needs to be ensured, so that the particle size of the resin bonding material needs to be limited.
Preferably, the solvent is at least one of diethylene glycol butyl ether, diethylene glycol methyl ether, terpineol, propylene glycol diacetate and isophorone; the additive comprises a dispersing agent, a defoaming agent and a leveling agent. The additive can be added in the self-temperature-limiting conductive ink in a suitable way, and when the performance of the self-temperature-limiting conductive ink is better, the additive can be even not added. The additive in the scheme comprises a dispersing agent, a defoaming agent and a leveling agent, wherein the dispersing agent can be polyacrylamide, the defoaming agent can be polyoxypropylene pentaerythritol ether, the leveling agent can be polyether polyester modified organic siloxane, and the additive also comprises a stabilizing agent and the like.
Preferably, the carbon-based conductive filling material has a Curie temperature of 70-90 ℃ and a room temperature resistivity of 100-180 omega cm.
Preferably, the pencil hardness of the self-temperature-limiting conductive ink is more than or equal to 2H; when the temperature of the self-temperature-limiting conductive ink is not lower than 30 ℃ and not higher than 40 ℃, the resistivity is 2.1-2.3 omega mm; when the temperature is less than or equal to 50 ℃ and less than 40 ℃, the resistivity is 2.3-2.8 omega mm; when the temperature is 50 ℃ or lower and is less than or equal to 60 ℃, the resistivity is 2.8-3.7 omega mm; when the temperature is less than or equal to 70 ℃ and less than 60 ℃, the resistivity is 3.7-4.9 omega mm; when the temperature is 70 ℃ or less and 80 ℃, the resistivity is 4.9-6.7; when the temperature is 80 ℃ or less and 110 ℃, the resistivity is 6.7-8.5 omega mm.
In addition, the invention also provides a preparation method of the self-temperature-limiting conductive ink, which comprises the following steps:
s1, mixing a carbon-based conductive filling material, a self-temperature-limiting material, a resin bonding material, an additive and a solvent according to mass percentage, and then carrying out ball milling for more than 1h to fully grind and disperse the mixture until the particle size of the mixture is less than 10um, so as to obtain the self-temperature-limiting conductive ink;
the viscosity of the self-temperature-limiting conductive ink is 80-120 pa · s.
Besides the independent particle size of each raw material in the self-temperature-limiting conductive ink, the obtained self-temperature-limiting conductive ink finished product needs to be subjected to ball milling and crushing, so that the particle size of the finished product is ensured to be in an appropriate range, and a good printing effect is obtained. The viscosity of the finished self-temperature-limiting conductive ink product in the scheme can be controlled within the range of 80-120 pa · s.
When the foam of the finished self-temperature-limiting conductive ink is too large or too viscous, 1% of defoaming agent can be continuously added and uniformly stirred, and then the mixture is sieved by a 400-mesh sieve, and a small amount of solvent is added and uniformly stirred by a homogenizer.
Preferably, the preparation process of the self-temperature-limiting material comprises the following steps:
s11, according to mass percent, mixing BaTiO3、SrTiO3、Cr2O3、La2O3、CaCO3、SiO2And Al2O3After mixing, adding 0.02-0.05% of PVA, 0.3-0.8% of lignin and 0.42-0.85% of sodium metasilicate by mass, adding water, and performing ball milling for 10 hours to obtain slurry, wherein the mass ratio of the material to the grinding balls to the water is 1:1:2 during ball milling;
s12, performing spray granulation on the ball-milled slurry, screening the ball-milled slurry by a 100-mesh screen to obtain powder, and pressing the powder to obtain a blank;
s13, pre-sintering the blank for 30min, and then sintering at the sintering temperature of 1295-1305 ℃ to obtain a semi-finished product;
the pre-sintering process comprises the following steps: burning at 100-120 deg.c for 30min and at 250-300 deg.c for 30 min;
s14, crushing the semi-finished product, adding water, ball-milling for 5-10 min, drying, granulating, and sieving with a 325-mesh sieve to obtain the self-temperature-limiting material. The self-temperature-limiting material has larger particle size, and needs to be crushed and ground into powder by a grinding machine and then ball-milled to reduce the particle size, so that the influence on the performance of the self-temperature-limiting conductive material caused by a large amount of lost ball stone particles brought by overlong ball-milling time is avoided. The addition of PVA, lignin and sodium metasilicate can promote the ball milling effect of each raw material, so that the granularity of the raw materials is lower, the dispersion effect is better, and the prepared self-temperature-limiting conductive ink has better quality.
The invention also provides a heating ceramic which is prepared by screen printing the self-temperature-limiting conductive ink on a ceramic tile, wherein the heating temperature of the ceramic tile is 25-58 ℃. The self-temperature-limiting conductive ink can be directly applied to a ceramic tile substrate through a printing process, so that the problem of thermal attenuation caused by a PET (polyethylene terephthalate) film is solved, the temperature of heating ceramic can be comprehensively limited, and overheating is prevented.
Preparing a ceramic tile with a preset groove; printing self-temperature-limiting conductive ink in a preset groove of the ceramic tile, drying at 180 ℃ for 30min, and then drying at 300 ℃ for 30min to enable the resistance of the self-temperature-limiting conductive ink to tend to be stable; printing two pieces of conductive silver paste in a region tightly attached to the self-temperature-limiting conductive ink in the preset groove, curing at 120 ℃, and covering a conductive copper foil electrode on the conductive silver paste (a solder point is arranged at the positive electrode and the negative electrode of the copper foil to lead out a lead); applying an insulating layer (resin) on the surface of the structure; and arranging a polyurethane heat-insulating layer for pressing. The above is one of the methods for producing the heat-generating ceramic, and the above parameters and the components used may be adjusted adaptively in other embodiments.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. according to the invention, the special self-temperature-limiting material is added in the formula of the conductive ink, so that the conductive ink has a self-temperature-limiting function, the source of the self-temperature-limiting material is wide, the introduction process is simple, the point expansion can be realized to the surface, the temperature limitation can be comprehensively carried out on the thin film resistor, and the circuit damage and the thermal attenuation caused by circuit overheating can be prevented. The prepared self-temperature-limiting conductive ink has a remarkable temperature control effect, the resistance value can be rapidly increased under a high-temperature condition, and the self-temperature-limiting conductive ink effectively stops heating in the temperature range, so that the heating temperature of heating ceramic is not higher than 120 ℃, and the resin bonding material cannot be melted in the heating ceramic due to the higher melting point of the resin bonding material, so that the influence on the internal structure of the heating ceramic tile is small, and the long-term use can be maintained.
2. According to the invention, the high-temperature-resistant polytetrafluoroethylene resin or polyimide resin is used as the resin bonding material, so that the softening point of the film resistor formed by drying the conductive ink is high, the film resistor can be directly applied to a ceramic tile substrate to prepare the heating ceramic, and the film resistor can be dried and bonded with the conductive silver paste at 100-300 ℃, so that the circuit cannot be damaged even if the heating ceramic is overheated, and the phenomenon of thermal attenuation cannot occur basically.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph showing the trend of the power of a heat-generating ceramic with temperature in example 1 of the self-temperature-limited conductive ink provided herein;
FIG. 2 is a graph showing the trend of the power of a heat-generating ceramic with temperature in example 2 of the self-temperature-limited conductive ink provided herein;
FIG. 3 is a graph showing the trend of the power of the heat-generating ceramic with temperature in example 3 of the self-temperature-limited conductive ink provided by the present application.
The implementation, functional features and advantages of the objectives of the present application will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
A preparation method of self-temperature-limiting conductive ink comprises the following steps:
s1, mixing a carbon-based conductive filling material, a self-temperature-limiting material, a resin bonding material, an additive and a solvent according to the mass percentage of 18-45% of the carbon-based conductive filling material, 6-10% of the self-temperature-limiting material, 20-48% of the resin bonding material, 3-6% of the additive and 25-45% of the solvent, and then carrying out ball milling for more than 1h to fully grind and disperse the mixture until the particle size of the mixture is less than 10 mu m, thereby obtaining the self-temperature-limiting conductive ink;
the carbon-based conductive filling material is at least one of graphene, nano carbon powder and carbon nano tubes; the resin bonding material is resin with a melting point of more than 320 ℃, and the particle size of the resin bonding material is 3-10 mu m; the solvent is at least one of diethylene glycol butyl ether, diethylene glycol methyl ether, terpineol, propylene glycol diacetate and isophorone; the additive comprises a dispersing agent, a defoaming agent and a leveling agent.
The viscosity of the self-temperature-limiting conductive ink is 80-120 pa · s;
the preparation process of the self-temperature-limiting material comprises the following steps:
s11, pressing BaTiO3 41%～65%、SrTiO327％～50%、Cr2O3 5％～9%、La2O3 3％～7%、CaCO30.5％～1%、SiO2 0.4％～1%、Al2O30.1 to 0.5 percent of BaTiO3 、SrTiO3、Cr2O3、La2O3、CaCO3、SiO2、Al2O3After mixing, wherein, BaTiO3、SrTiO3、Cr2O3And La2O3The mass ratio of (1): (0.45-1): (0.1-0.23): (0.05-0.15), adding PVA with the mass fraction of 0.02%, lignin with the mass fraction of 0.4% and sodium metasilicate with the mass fraction of 0.69%, adding water and ball-milling for 10 hours to obtain slurry;
s12, performing spray granulation on the ball-milled slurry, screening the ball-milled slurry by a 100-mesh screen to obtain powder, and pressing the powder to obtain a blank;
s13, pre-sintering the blank for 30min, and then sintering at the sintering temperature of 1295-1305 ℃ to obtain a semi-finished product;
the pre-sintering process comprises the following steps: burning at 100-120 deg.c for 30min and at 250-300 deg.c for 30 min;
s14, crushing the semi-finished product, adding water, rapidly ball-milling for 5min by using a star ball-milling tank, drying, granulating, and sieving by using a 325-mesh sieve to obtain the self-temperature-limiting material.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
Example 1
A preparation method of self-temperature-limiting conductive ink comprises the following steps:
s1, mixing 27% of carbon-based conductive filling material, 8% of self-temperature-limiting material, 30% of resin bonding material, 3% of additive (1% of dispersant, 2% of flatting agent), 32% of solvent (10% of terpineol and 22% of propylene glycol diacetate) according to mass percent, and then carrying out ball milling for more than 1h to fully grind and disperse the mixture until the particle size of the mixture is less than 10um, thus obtaining the self-temperature-limiting conductive ink;
the carbon-based conductive filling material comprises 30% of graphene, 30% of nano carbon powder and 40% of carbon nano tubes;
the preparation process of the self-temperature-limiting material comprises the following steps:
s11, mixing 56% of BaTiO according to mass percentage3、32% SrTiO3、6% Cr2O3、4%La2O3、0.7% CaCO3、0.8% SiO2And 0.5% Al2O3After mixing, BaTiO3 and SrTiO3、Cr2O3And La2O3The mass ratio of (1): 0.57: 0.11: 0.07, adding PVA with the mass fraction of 0.02%, lignin with the mass fraction of 0.4% and sodium metasilicate with the mass fraction of 0.69%, adding water and carrying out ball milling for 10 hours to obtain slurry;
s12, performing spray granulation on the ball-milled slurry, screening the ball-milled slurry by a 100-mesh screen to obtain powder, and pressing the powder to obtain a blank;
s13, pre-sintering the blank for 30min, and then sintering at 1295 ℃ to obtain a semi-finished product;
the pre-sintering process comprises the following steps: burning at 110 deg.C for 30min, and then at 268 deg.C for 30 min;
s14, crushing the semi-finished product, adding water, ball-milling for 5min, drying, granulating, and sieving by a 325-mesh sieve to obtain the self-temperature-limiting material.
Example 2
A preparation method of self-temperature-limiting conductive ink comprises the following steps:
s1, mixing 24% of carbon-based conductive filling material, 7% of self-temperature-limiting material, 24% of resin bonding material, 2% of additive (0.5% of dispersant, 1.5% of flatting agent) and 43% of solvent (8% of isophorone and 35% of diethylene glycol butyl ether) according to mass percentage, and then carrying out ball milling for more than 1h to fully grind and disperse the mixture until the particle size of the mixture is less than 10um, thereby obtaining the self-temperature-limiting conductive ink;
the carbon-based conductive filling material is graphene and nano carbon powder, and the mass ratio of the graphene to the nano carbon powder is 1.5: 1;
the preparation process of the self-temperature-limiting material comprises the following steps:
s11, according to mass percent, mixing 48 percent of BaTiO3、38% SrTiO3、7% Cr2O3、5%La2O3、0.7% CaCO3、1% SiO2And 0.3% Al2O3After mixing, BaTiO3 and SrTiO3、Cr2O3And La2O3The mass ratio of (1): 0.79: 0.15: 0.10, adding PVA with the mass fraction of 0.04%, lignin with the mass fraction of 0.65% and sodium metasilicate with the mass fraction of 0.8%, adding water and carrying out ball milling for 10 hours to obtain slurry;
s12, performing spray granulation on the ball-milled slurry, screening the ball-milled slurry by a 100-mesh screen to obtain powder, and pressing the powder to obtain a blank;
s13, pre-sintering the blank for 30min and then sintering, wherein the sintering temperature is 1301 ℃, and obtaining a semi-finished product;
the pre-sintering process comprises the following steps: burning at 108 deg.C for 30min, and then at 290 deg.C for 30 min;
s14, crushing the semi-finished product, adding water, ball-milling for 7min, drying, granulating, and sieving by a 325-mesh sieve to obtain the self-temperature-limiting material.
Example 3
A preparation method of self-temperature-limiting conductive ink comprises the following steps:
s1, mixing 24% of carbon-based conductive filling material, 9% of self-temperature-limiting material, 28% of resin bonding material, 3% of additive (1% of dispersant, 2% of leveling agent) and 36% of solvent (11% of propylene glycol diacetate and 25% of propylene glycol diacetate) according to mass percent, and then carrying out ball milling for more than 1h to fully grind and disperse the mixture until the particle size of the mixture is less than 10um, thus obtaining the self-temperature-limiting conductive ink;
the carbon-based conductive filling material is graphene and carbon nano tubes, and the mass ratio of the graphene to the carbon nano tubes is 1: 1;
the preparation process of the self-temperature-limiting material comprises the following steps:
s11, mixing 52% of BaTiO according to mass percentage3、39% SrTiO3、5% Cr2O3、3%La2O3、0.5% CaCO3、0.4% SiO2And 0.1% Al2O3After mixing, in which BaTiO3、SrTiO3、Cr2O3And La2O3The mass ratio of (1): 0.75: 0.10: 0.06, adding PVA with the mass fraction of 0.04%, lignin with the mass fraction of 0.5% and sodium metasilicate with the mass fraction of 0.52%, adding water and carrying out ball milling for 10 hours to obtain slurry;
s12, performing spray granulation on the ball-milled slurry, screening the ball-milled slurry by a 100-mesh screen to obtain powder, and pressing the powder to obtain a blank;
s13, pre-sintering the blank for 30min, and then sintering at the sintering temperature of 1295-1305 ℃ to obtain a semi-finished product;
the pre-sintering process comprises the following steps: baking at 117 deg.C for 30min, and baking at 250 deg.C for 30 min;
s14, crushing the semi-finished product, adding water, ball-milling for 10min, drying, granulating, and sieving by a 325-mesh sieve to obtain the self-temperature-limiting material.
Example 4
The conditions in this example are the same as in example 3, except that: the mass percentage of the self-temperature-limiting material in the embodiment is 55 percent of BaTiO3、33% SrTiO3、6% Cr2O3、4%La2O3、0.8% CaCO3、0.7% SiO2And 0.5% Al2O3In which BaTiO3、PbTiO3、SiO2And Al2O3The mass ratio of (1): 0.6: 0.11: 0.07.
comparative example 1
The comparative example was conducted under the same conditions as in example 3 except that: the mass percentage of the self-temperature-limiting material in the comparative example is 40 percent of BaTiO3、42% SrTiO3、9% Cr2O3、7%La2O3、1% CaCO3、0.5% SiO2And 0.5% Al2O3In which BaTiO3、SrTiO3、SiO2And Al2O3The mass ratio of (1): 1.05: 0.23: 0.18.
comparative example 2
The comparative example was conducted under the same conditions as in example 3 except that: the mass percentage of the self-temperature-limiting material in the comparative example is 37 percent of BaTiO3、43% SrTiO3、12% Cr2O3、2%La2O3、2% CaCO3、3% SiO2And 1% of Al2O3In which BaTiO3、SrTiO3、SiO2And Al2O3The mass ratio of (1): 1.16: 0.32: 0.05.
comparative example 3
The comparative example was conducted under the same conditions as in example 3 except that: the mass percentage of the self-temperature-limiting material in the comparative example is 60 percent of BaTiO3、25% SrTiO3、4% Cr2O3、10%La2O3、0.3% CaCO3、0.2% SiO2And 0.5% Al2O3In which BaTiO3、SrTiO3、SiO2And Al2O3The mass ratio of (1): 0.42: 0.07: 0.17.
example 5
The conditions in this example are the same as in example 4, except that: the carbon-based conductive filling material comprises the following raw materials in percentage by mass: 33% of graphene, 28% of nano carbon powder and 39% of carbon nano tubes.
Comparative example 4
The comparative example was conducted under the same conditions as in example 3 except that: the resin adhesive is replaced by ternary hydroxychlorovinyl acetate resin with low melting point (114 ℃).
Comparative example 5
In the comparative example, the heating power change and the thermal attenuation were tested under a uniform test environment using a commercially available graphene heating ceramic.
The heat-generating ceramics prepared by the self-temperature-limiting conductive inks of examples 1 to 5 and comparative examples 1 to 5 (wherein, only the thermal decay rate was detected in comparative example 5) were used for the examination (the methods for preparing the heat-generating ceramics were kept the same for the three): printing self-temperature-limiting conductive ink in a preset groove of the ceramic tile, drying at 180 ℃ for 30min, and then drying at 300 ℃ for 30min to enable the resistance of the self-temperature-limiting conductive ink to tend to be stable; printing two pieces of conductive silver paste in a region tightly attached to the self-temperature-limiting conductive ink in the preset groove, curing at 120 ℃, and covering a conductive copper foil electrode on the conductive silver paste (a solder point is arranged at the positive electrode and the negative electrode of the copper foil to lead out a lead); applying an insulating layer (resin) on the surface of the structure; and arranging a polyurethane heat-insulating layer for pressing.
The performance detection method comprises the following steps: the heating ceramic is arranged in an insulation box isolated from the outside (made of a polyurethane insulation board, the temperature inside the insulation box can be kept constant, and the influence of the outside temperature is small).
1. And (3) detecting the PTC effect: and connecting a power supply, and connecting two ends of the electrode by using an Ulidrute 9800 intelligent electrical parameter detector. The power detection of the heating ceramic in the scheme comprises two stages, wherein the first stage is that the temperature is less than or equal to 56 ℃, and the heating ceramic can perform self heating at the moment; the second stage is that the temperature is greater than 56 ℃, a temperature detector is arranged in the heat preservation box, the temperature detector detects that the heating ceramic does not continue to heat due to the self-temperature-limiting conductive ink along with the increase of time, and the temperature is always kept at about 56 ℃; therefore, in order to further detect the heating effect of the heating ceramic when the temperature is above 56 ℃, an external heat source is introduced to heat the heating ceramic, the heating rate of the external heat source is increased by 1 ℃ per minute, the temperature is gradually increased, the power is detected, the value of the power is detected at least every 5 ℃, and a curve is drawn.
2. Detecting the thermal attenuation rate: the initial heat generation power of the brick surface temperature of the sample is detected by instruments such as an ammeter and the like at 27 ℃ (close to normal temperature and slightly higher than normal temperature), after the continuous work is carried out for 300 hours, the heat generation power of the brick surface temperature of the sample is detected by an Ullidute 9800 intelligent electrical parameter detector at 27 ℃, and the heat generation power attenuation rate of the sample is calculated.
PTC effect test result table
In the scheme, the size of the resistor is confirmed by testing power, and the voltage of the heating ceramic is kept constant through the formula P = U2It is known that the lower the power, the higher the resistance, and from the results of the tests of examples 1 to 5, the power is gradually decreased (i.e. the resistance is gradually increased) with the gradual increase of the temperature, and the self-heating effect of the heating ceramic is decreased due to the decrease of the power, and even the operation is stopped (the heating operation is basically stopped when the power is less than 1W), wherein the heating power of example 1 is 0.4W at 103 ℃; example 2 the heating power was already 0.5W at 100 ℃; example 3 the heating power at 100 ℃ was 0.4W; example 4 the heating power at 95 ℃ was 0.5W; in example 5, the heating power is 0.3W at 95 ℃, the self-temperature limiting effect is excellent in examples 4 and 5, particularly the self-temperature limiting effect is better under a relatively high temperature condition, local temperature is overhigh in the case of short circuit of the heating ceramic, and the excellent temperature control effect of the self-temperature-limiting conductive ink can prevent overheating and avoid damage. After the component proportion of the self-temperature-limiting material is adjusted, the detection results of the comparative examples 1 to 3 show that the self-temperature-limiting effect is reduced. The power of comparative example 4 was not measured, but mainly due to unstable adhesion of the ternary hydroxychlorovinyl acetate resin, short circuit occurred, and the likeBecoming a safe accident.
Thermal attenuation rate test result table
As can be seen from the above table, the self-temperature-limiting conductive ink has a low power thermal decay rate, and after 300 hours of use, the power thermal decay rate of the examples 1-5 is below 1%, and the thermal decay rate of the examples 4-5 is even 0; the thermal decay rates of comparative examples 1 to 3 were all 1.5% or more, wherein the thermal decay rate of comparative example 1 was even 4.79%, and the heat generation efficiency was greatly reduced. In long-term use, the efficiency of generating heat of the pottery that generates heat in this scheme can not produce and reduce by a wide margin, influences the result of use.
Examples 1 to 5 and comparative examples 1 to 4 were tested for the remaining properties, and the results are shown in the following table:
results of remaining Performance test
As can be seen from the detection results in the table above, the heating ceramic prepared by the self-temperature-limiting conductive ink has a good self-temperature-limiting effect, the printing effect of the self-temperature-limiting conductive ink during printing is also good, the viscosity can be controlled within the range of 92-98pa · s, and the hardness of the self-temperature-limiting conductive ink can be maintained at about 3H.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. The self-temperature-limiting conductive ink is characterized by comprising the following raw materials in percentage by mass: 18-45% of carbon-based conductive filling material, 6-10% of self-temperature-limiting material, 20-48% of resin bonding material, 3-6% of additive and 25-45% of solvent;
the self-temperature-limiting material is prepared from the following raw materials in percentage by mass: BaTiO 23 41%～65%、SrTiO327％～50%、Cr2O3 5％～9%、La2O3 3％～7%、CaCO3 0.5％～1%、SiO2 0.4％～1%、Al2O3 0.1％～0.5%；
Wherein, BaTiO3、SrTiO3、Cr2O3And La2O3The mass ratio of (1): (0.45-1): (0.1-0.23): (0.05-0.15).
2. The self-temperature-limiting conductive ink as claimed in claim 1, wherein the carbon-based conductive filler material is at least one of graphene, nano carbon powder and carbon nanotubes.
3. The self-temperature-limiting conductive ink as claimed in claim 1, wherein the carbon-based conductive filling material is prepared from the following raw materials in percentage by mass: 33% of graphene, 28% of nano carbon powder and 39% of carbon nano tubes.
4. The self-temperature-limiting conductive ink as claimed in claim 1, wherein the resin binder is a resin with a melting point of more than 320 ℃, and the particle size of the resin binder is 3-10 μm.
5. The self temperature limiting conductive ink of claim 4, wherein the solvent is at least one of diethylene glycol butyl ether, diethylene glycol methyl ether, terpineol, propylene glycol diacetate, and isophorone;
the additive comprises a dispersing agent, a defoaming agent and a leveling agent.
6. The self-temperature-limited conductive ink as claimed in claim 1, wherein the carbon-based conductive filler has a Curie temperature of 70 to 90 ℃ and a room temperature resistivity of 100 to 180 Ω -cm.
7. The self-temperature-limiting conductive ink as claimed in claim 1, wherein the pencil hardness of the self-temperature-limiting conductive ink is not less than 2H;
when the temperature of the self-temperature-limiting conductive ink is not lower than 30 ℃ and not higher than 40 ℃, the resistivity is 2.1-2.3 omega mm; when the temperature is less than or equal to 50 ℃ and less than 40 ℃, the resistivity is 2.3-2.8 omega mm; when the temperature is 50 ℃ or lower and is less than or equal to 60 ℃, the resistivity is 2.8-3.7 omega mm; when the temperature is less than or equal to 70 ℃ and less than 60 ℃, the resistivity is 3.7-4.9 omega mm; when the temperature is less than or equal to 70 ℃ and less than or equal to 80 ℃, the resistivity is 4.9-6.7 omega mm; when the temperature is 80 ℃ or less and 110 ℃, the resistivity is 6.7-8.5 omega mm.
8. A method for preparing a self-temperature-limiting conductive ink, which is characterized in that the method for preparing the self-temperature-limiting conductive ink as claimed in any one of claims 1 to 7 comprises the following steps:
s1, mixing a carbon-based conductive filling material, a self-temperature-limiting material, a resin bonding material, an additive and a solvent according to mass percentage, and then carrying out ball milling for more than 1h to fully grind and disperse the mixture until the particle size of the mixture is less than 10um, so as to obtain the self-temperature-limiting conductive ink;
the viscosity of the self-temperature-limiting conductive ink is 80-120 pa · s.
9. The method for preparing the self-temperature-limiting material according to claim 8, wherein the preparation process of the self-temperature-limiting material comprises the following steps:
s11, according to mass percent, mixing BaTiO3、SrTiO3、Cr2O3、La2O3、CaCO3、SiO2And Al2O3After mixing, adding 0.02-0.05% of PVA, 0.3-0.8% of lignin and 0.42-0.85% of sodium metasilicate by mass, adding water and ball-milling for more than 10 hours to obtain slurry;
s12, performing spray granulation on the ball-milled slurry, screening the ball-milled slurry by a 100-mesh screen to obtain powder, and pressing the powder to obtain a blank;
s13, pre-sintering the blank for 30min, and then sintering at the sintering temperature of 1295-1305 ℃ to obtain a semi-finished product;
the pre-sintering process comprises the following steps: burning at 100-120 deg.c for 30min and at 250-300 deg.c for 30 min;
s14, crushing the semi-finished product, adding water, ball-milling for 5-10 min, drying, granulating, and sieving with a 325-mesh sieve to obtain the self-temperature-limiting material.
10. A heat-generating ceramic prepared by screen printing the self-temperature-limited conductive ink as claimed in any one of claims 1 to 7 on a ceramic tile.
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