CN112309606A - Composite metal slurry composition and preparation method and application thereof - Google Patents
Composite metal slurry composition and preparation method and application thereof Download PDFInfo
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- CN112309606A CN112309606A CN201910701113.7A CN201910701113A CN112309606A CN 112309606 A CN112309606 A CN 112309606A CN 201910701113 A CN201910701113 A CN 201910701113A CN 112309606 A CN112309606 A CN 112309606A
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- 239000000203 mixture Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 title abstract description 14
- 239000002184 metal Substances 0.000 title abstract description 14
- 239000002131 composite material Substances 0.000 title abstract description 5
- 239000002002 slurry Substances 0.000 title description 2
- 239000000654 additive Substances 0.000 claims abstract description 39
- 230000000996 additive effect Effects 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000007769 metal material Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 22
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- CYKMNKXPYXUVPR-UHFFFAOYSA-N [C].[Ti] Chemical compound [C].[Ti] CYKMNKXPYXUVPR-UHFFFAOYSA-N 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims description 33
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 229940116411 terpineol Drugs 0.000 claims description 6
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011195 cermet Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 17
- 239000000919 ceramic Substances 0.000 abstract description 14
- 229910010293 ceramic material Inorganic materials 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 238000003801 milling Methods 0.000 description 4
- -1 titanium carbide compound Chemical class 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ZCSHACFHMFHFKK-UHFFFAOYSA-N 2-methyl-1,3,5-trinitrobenzene;2,4,6-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)C1NC([N+]([O-])=O)NC([N+]([O-])=O)N1.CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O ZCSHACFHMFHFKK-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
Abstract
The invention provides a composite metal paste composition and a preparation method thereof, the electronic paste composition comprises a base material, a heating metal material, an additive, porcelain powder and an organic carrier, wherein the base material is selected from at least one of titanium-carbon compound and graphene, the metal heating material is selected from at least one of tungsten, nickel, cobalt and chromium, and the additive is selected from at least one of ruthenium, tellurium, germanium, vanadium, yttrium and iridium; the method comprises the following steps: the base material, the heat-generating metal material, the porcelain powder and the additive are mixed, and then the resulting mixture is brought into contact with the organic vehicle. The invention also provides application of the electronic paste composition in preparing a metal ceramic heating element with low resistance temperature coefficient. The electronic paste composition of the present invention and the electronic paste prepared by the above method of the present invention have a uniform and low temperature coefficient of resistance. When the ceramic material is applied to a metal ceramic heating body, the resistance of a sintered product can be ensured to be slightly changed by temperature in the use process.
Description
Technical Field
The invention belongs to the field of electronic paste, and particularly relates to a composite metal paste composition, and a preparation method and application thereof.
Background
As a novel material, the electronic paste is far superior to traditional circuit equipment (such as resistance wires, electric heating tubes and the like), has the characteristics of environmental protection, high efficiency, energy conservation and the like, has the cost close to that of the traditional material, and can be a main application direction in the future undoubtedly. Various types of Au, Ag and complex-doped noble metal conductive pastes have been developed, but they are expensive, have low adhesion strength to a base material, and are likely to cause an electron transfer phenomenon when used for conductive tapes of thick film circuits and electrode terminal materials of capacitors, thereby reducing the conductivity of the conductive pastes, although they are excellent in conductivity.
Graphene has excellent optical, electrical and mechanical properties, and is one of the highest known materials, and also has good toughness and very good heat conduction performance. Meanwhile, the titanium carbide compound serving as a high-temperature structural material has good high-temperature mechanical property and excellent oxidation resistance. At present, the demand for novel high-performance electronic paste in China is increasing. Although various electronic paste products exist in the prior art, electronic components manufactured by the electronic paste in the prior art have the defect of great resistance temperature coefficient deviation due to different batches, so that the resistance control difficulty is extremely high, the defective rate of the produced products is extremely high, the error of the product resistance temperature coefficient is very large, and the circuit program cannot accurately control the temperature. In addition, it is difficult for existing electronic paste products to achieve a low temperature coefficient of resistance while ensuring satisfactory temperature coefficient of resistance errors.
Disclosure of Invention
The invention aims to solve the technical problem that the product prepared by the existing electronic paste is difficult to achieve low resistance temperature coefficient while ensuring that the resistance temperature coefficient error of each batch is very small. The inventors of the present invention have conducted extensive experiments to very surprisingly find that products made from certain components of electronic pastes have incredibly consistent temperature coefficients of resistance in batches, and that the temperature coefficients of resistance are satisfactorily low, thereby completing the present invention.
In order to achieve the above object, in one aspect, the present invention provides an electronic paste composition, wherein the electronic paste composition comprises a base material, a heat-generating metallic material, an additive, a porcelain powder, and an organic vehicle, and wherein the base material is selected from at least one of titanium-carbon compounds and graphene, the heat-generating metallic material is selected from at least one of tungsten, nickel, cobalt, and chromium, and the additive is selected from at least one of ruthenium, tellurium, germanium, vanadium, yttrium, and iridium.
In a preferred embodiment of the present invention, the weight ratio of the base material and the heat-generating metal material is 0.5:9.5 to 9.5: 0.5.
In a preferred embodiment of the invention, the titanium carbide compound is titanium aluminum carbide, titanium silicon carbide or a combination thereof.
In a preferred embodiment of the present invention, the content of the additive is 0.5 to 10% by weight, preferably 1 to 6% by weight, based on the total weight of the base material and the heat-generating metal material.
In a preferred embodiment of the present invention, the content of the porcelain powder is 0.5 to 8% by weight, and preferably, the content of the porcelain powder is 0.8 to 5% by weight, based on the total weight of the base material and the heat-generating metal material.
In a preferred embodiment of the present invention, the organic vehicle is a mixture of terpineol, ethyl cellulose, glycerin and absolute ethyl alcohol, and preferably, the content of the organic vehicle is 5 to 30% by weight based on the total weight of the base material and the heat-generating metal material.
In another aspect, the present invention provides a method for preparing the above electronic paste composition, wherein the method comprises: the base material, the heat-generating metal material, the porcelain powder and the additive are mixed, and then the resulting mixture is brought into contact with the organic vehicle.
In a preferred embodiment of the invention, the contacting is ball milling in a ball mill, preferably at a speed of 100-.
In a preferred embodiment of the invention, absolute ethanol is used as the milling medium in the ball mill, preferably in a weight ratio of mixture to milling medium of 1:1 to 1: 4.
In a preferred embodiment of the present invention, the obtained electronic paste composition has a particle size of 200-500 mesh and a viscosity of 10-100 pas.
In still another aspect, the present invention also provides the use of the above-mentioned electronic paste composition and the electronic paste composition prepared by the above-mentioned method for preparing a cermet heat-generating body having a low temperature coefficient of resistance.
In view of the foregoing, the electronic paste composition of the present invention provides unexpected characteristics that the temperature coefficient of resistance of products (e.g., heat generating elements) produced therefrom is unexpectedly consistent and low from batch to batch, so that the resistance control thereof becomes abnormally easy, and the production product failure rate is extremely low. When the electronic paste is applied to a metal ceramic heating element, the excellent performance of unexpectedly consistent and low resistance temperature coefficient can be obtained, the consistent resistance temperature coefficient of each batch of finished products can be ensured, the resistance is subjected to small temperature change in the using process, and therefore, the circuit is simple, and the overall heating reliability is high.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As used herein, the term "electronic paste" is a basic material for manufacturing a cermet heating element, and is a paste formed by uniformly mixing solid powder and a liquid solvent through three-roll rolling, wherein the electronic paste may be classified into a dielectric paste, a resistance paste, and a conductor paste according to the purpose; according to different types of substrates, the electronic paste can be further divided into ceramic substrates, polymer substrates, glass substrates, metal insulation substrate electronic paste and the like; according to different sintering temperatures, the electronic paste can be divided into high-temperature, medium-temperature and low-temperature drying electronic pastes; electronic paste can be divided into general electronic paste and special electronic paste according to different purposes; electronic paste can be divided into precious metal electronic paste and base metal electronic paste according to the price of the conductive phase.
As used herein, the term "temperature coefficient of resistance" (TCR) refers to the relative change in resistance (i.e., the rate of change in resistance with respect to the resistance) when the temperature changes by 1 degree, and is calculated as TCR (R ═ R)T2-RT1)/[(T2-T1)×RT1]In ppm/DEG C, where T1Denotes a first temperature, T2Denotes the second temperature, RT1Represents a resistance value at a first temperature, RT2Representing the resistance value at the second temperature. The temperature coefficient of resistance is a parameter closely related to the microstructure of the metal, which has a theoretical maximum without any defects. That is, the magnitude of the temperature coefficient of resistance itself characterizes the performance of the metal process to some extent. In the development process or on-line monitoring of a new technology process, the reliability of metal can be monitored early and evaluated quickly by using the temperature coefficient of resistance.
In one aspect, the present invention provides an electronic paste composition, wherein the electronic paste composition may include a base material, a heat-generating metallic material, an additive, a porcelain powder, and an organic vehicle, and wherein the base material may be selected from at least one of a titanium-carbon compound and graphene, the metallic heat-generating material may be selected from at least one of tungsten, nickel, cobalt, and chromium, and the additive may be selected from at least one of ruthenium, tellurium, germanium, vanadium, yttrium, and iridium.
According to the present invention, the contents of the base material and the heat-generating metal material in the electronic paste composition of the present invention are not particularly limited, and may be those commonly used in the art. In a preferred embodiment, the weight ratio of the base material and the heat-generating metal material may be 0.5:9.5 to 9.5: 0.5; more preferably, the weight ratio of the base material and the heat-generating metal material may be 1:9 to 9: 1. In another preferred embodiment, the titanium carbon compound may be titanium aluminum carbide, titanium silicon carbide, or a combination thereof.
In addition, through the research of the present inventors, it was found that the temperature coefficient of resistance of the electronic paste can be advantageously greatly reduced by adding the additive of the present invention (e.g., at least one of ruthenium, tellurium, germanium, vanadium, yttrium, and iridium) to the conventional composite type metal paste in the art. In a preferred embodiment, the additive may be contained in an amount of 0.5 to 10 wt% based on the total weight of the base material and the heat-generating metal material; more preferably, the content of the additive may be 1 to 6% by weight. In a preferred embodiment, the content of the porcelain powder is 0.5 to 8% by weight, and preferably, the content of the porcelain powder is 0.8 to 5% by weight, based on the total weight of the base material and the heat-generating metal material.
According to the present invention, the kind and content of the organic vehicle in the electronic paste composition of the present invention are not particularly limited, and may be those commonly used in the art. In a preferred embodiment, the organic vehicle may be a mixture of terpineol, ethylcellulose, glycerol and absolute ethanol, such as 90-95 wt% (e.g., 92 wt%) terpineol, 3-5 wt% (e.g., 5 wt%) ethylcellulose, 1-5 wt% (e.g., 2 wt%) glycerol and 1-3 wt% (e.g., 1 wt%) absolute ethanol, and preferably, the content of the organic vehicle may be 5-30 wt%, preferably 10-20 wt%, based on the total weight of the base material and the heat-generating metal material.
In another aspect, the present invention provides a method for preparing the above electronic paste composition, wherein the method comprises: the base material, the heat-generating metal material, the porcelain powder and the additive are mixed, and then the resulting mixture is brought into contact with the organic vehicle.
According to the present invention, the mixing of the base material, the heat-generating metallic material, the porcelain powder and the additive may be performed in any order, for example, the base material and the heat-generating metallic material may be mixed first, and then the porcelain powder and the additive may be mixed, or the four may be directly mixed, etc. In the case of contacting the resulting mixture with the organic vehicle, in order to make the mixture more uniform, the mixture may be stirred or ball-milled while being contacted with the organic vehicle. In a preferred embodiment, the contacting may be ball milling in a ball mill (e.g., a planetary ball mill).
According to the present invention, there is no particular limitation on the conditions of ball milling, and ball milling conditions conventional in the art may be used as long as the mixture can be sufficiently contacted with the organic vehicle. In a preferred embodiment, the speed of the ball milling can be 100-. In another preferred embodiment, the ball milling speed may be 400-500r/min and the time may be 1.5-3 h. In addition, as the ball milling medium used in the ball milling, a ball milling medium conventional in the art may also be used. In a preferred embodiment, absolute ethanol may be used as the milling medium in the ball mill, and preferably the weight ratio of the mixture to the milling medium may be in the range of from 1:1 to 1:4 (e.g., 1: 1.5).
In the method of preparing an electronic paste composition of the present invention, the electronic paste composition may be prepared to have desired physical properties, as needed. In order to enhance the use performance of the electronic paste in coating and printing, after the mixture and the organic carrier are subjected to ball milling, the particle size of the obtained electronic paste composition is 200-500 meshes, the viscosity is 10-100 Pa.s, for example, the particle size is 250-400 meshes, and the viscosity is 20-80 Pa.s.
In still another aspect, the present invention also provides the use of the above-mentioned electronic paste composition and the electronic paste composition prepared by the above-mentioned method for preparing a cermet heat-generating body having a low temperature coefficient of resistance.
The electronic paste composition of the present invention provides unexpected characteristics that the temperature coefficient of resistance of products (e.g., heat generating elements) prepared therefrom is unexpectedly uniform and low from batch to batch, so that the resistance control thereof becomes abnormally easy, and the production product failure rate is extremely low. When the electronic paste is applied to a metal ceramic heating element, the excellent performance of unexpectedly consistent and low resistance temperature coefficient can be obtained, the consistent resistance temperature coefficient of each batch of finished products can be ensured, the resistance is subjected to small temperature change in the using process, and therefore, the circuit is simple, and the overall heating reliability is high.
The present invention will be described in detail below by way of examples.
In the following examples, a mixture of 92 wt% terpineol, 5 wt% ethylcellulose, 2 wt% glycerol and 1 wt% absolute ethanol was used as an organic vehicle, which was prepared by weighing the terpineol, ethylcellulose, glycerol and absolute ethanol in proportion and then uniformly mixing them by a magnetic stirrer at a water bath temperature of 90 ℃.
Example 1
Weighing 85 parts by weight of tungsten powder, 15 parts by weight of titanium aluminum carbide powder and 4 parts by weight of ceramic powder, uniformly mixing, mixing the mixed powder with 10 parts by weight of organic carrier, and putting the mixture into a planetary ball mill for ball milling, wherein absolute ethyl alcohol is used as a ball milling medium, the weight ratio of the mixture to the ball milling medium is 1.5:1, the ball milling speed is 500r/min, and the time is 1.5h, so that the electronic paste composition B0 is prepared.
Example 2
An electronic paste composition B1 was prepared in the same manner as in example 1, except that 1.5 parts by weight of germanium powder was added as an additive.
Example 3
An electronic paste composition B2 was prepared in the same manner as in example 1, except that 2.5 parts by weight of germanium powder was added as an additive.
Example 4
An electronic paste composition B3 was prepared in the same manner as in example 1, except that 3.5 parts by weight of germanium powder was added as an additive.
Example 5
An electronic paste composition B4 was prepared in the same manner as in example 1, except that 4.5 parts by weight of germanium powder was added as an additive.
The resistance values of the heat-generating elements obtained from the electronic paste compositions B0-B4 of examples 1-5 at 25 deg.C, 83 deg.C, 150 deg.C and 230 deg.C were measured, and the results are shown in Table 1, and then the resistance values of the respective examples were subjected to least squares and linear fitting to obtain temperature coefficients of resistance of examples 1-5, and the results are shown in Table 2.
TABLE 1
TABLE 2
Example 6
Electronic paste compositions C1 to C14 were prepared in the same manner as in example 1, with the contents shown in table 3, 5 batches each of which was prepared, and then the entire batches of the electronic paste compositions were each printed on a ceramic substrate by a technique conventional in the art, such as screen printing, to form a heat-generating element, and the temperature coefficient of resistance of the heat-generating element prepared from the batches of the electronic paste compositions was obtained in the same manner as the above measurement. For each of the electronic paste compositions C1-C14, 5 lots of average temperature coefficient of resistance (average TCR) were calculated from 5 lots of temperature coefficients of resistance TCR1, TCR2, TCR3, TCR4, and TCR5, and a deviation ratio of temperature coefficient of resistance TCR (TCRn — average TCR)/average TCR (n is 1, 2, 3, 4, or 5) for each lot were calculated, and further an average deviation ratio of temperature coefficient of resistance (average value of deviation ratios of temperature coefficients of resistance for 5 lots) for the 5 lots were calculated, and the results are shown in table 4.
TABLE 3
TABLE 4
As can be seen from the above examples, excellent heat generating elements can be prepared by the electronic paste composition (C3-C14) of the present invention such that the average deviation of the temperature coefficients of resistance between lots is significantly lower than that of heat generating elements prepared by the tungsten and titanium carbide compound electronic paste composition (C1-C2) alone, exhibiting excellent performance of uniform and low temperature coefficient of resistance.
Example 7
Weighing 89 parts by weight of tungsten powder, 11 parts by weight of graphene and 4 parts by weight of ceramic powder, uniformly mixing, mixing the mixed powder with 10 parts by weight of organic carrier, and putting the mixture into a planetary ball mill for ball milling, wherein absolute ethyl alcohol is used as a ball milling medium, the weight ratio of the mixture to the ball milling medium is 1.5:1, the ball milling speed is 500r/min, and the time is 1.5h, so that the electronic paste composition D0 is prepared.
Example 8
An electronic paste composition D1 was prepared in the same manner as in example 7, except that 1.5 parts by weight of vanadium powder was added as an additive.
Example 9
An electronic paste composition D2 was prepared in the same manner as in example 7, except that 2.5 parts by weight of vanadium powder was added as an additive.
Example 10
An electronic paste composition D3 was prepared in the same manner as in example 7, except that 3.5 parts by weight of vanadium powder was added as an additive.
Example 11
An electronic paste composition D4 was prepared in the same manner as in example 7, except that 4.5 parts by weight of vanadium powder was added as an additive.
The resistance values at 25 deg.C, 83 deg.C, 150 deg.C and 230 deg.C of the heat-generating elements obtained from the electronic paste compositions D0-D4 of examples 7-11 were measured, and the results are shown in Table 5, and then the resistance values of the respective examples were subjected to least squares and linear fitting to obtain temperature coefficients of resistance of examples 7-11, and the results are shown in Table 6.
TABLE 5
TABLE 6
Example 12
Electronic paste compositions E1 to E13 were prepared in the same manner as in example 7 in accordance with the contents shown in table 7, 5 batches of each electronic paste were prepared, and then the electronic paste compositions of the entire batches were each printed on a ceramic substrate by a technique conventional in the art such as screen printing to form a heat-generating element, and the temperature coefficient of resistance of the heat-generating element prepared from the electronic paste compositions of the batches was obtained in the same manner as the above measurement. For each of the electronic paste compositions E1-E13, 5 lots of average temperature coefficient of resistance (average TCR) were calculated from 5 lots of temperature coefficients of resistance TCR1, TCR2, TCR3, TCR4 and TCR5, and the deviation ratio of temperature coefficient of resistance TCR (TCRn-average TCR)/average TCR (n is 1, 2, 3, 4 or 5) for each lot were calculated, and further the average deviation ratio of temperature coefficient of resistance (average value of deviation ratios of temperature coefficients of resistance for 5 lots) for 5 lots was calculated, and the results are shown in Table 8.
TABLE 7
TABLE 8
As can be seen from the above examples, excellent heating elements can be prepared by the electronic paste composition (E2-E13) of the present invention such that the average deviation of the temperature coefficients of resistance between lots is significantly lower than that of the heating elements prepared by the tungsten and graphene electronic paste composition (E1) alone, showing excellent performance of uniform and low temperature coefficient of resistance.
Example 13
Weighing 87 parts by weight of nickel powder, 13 parts by weight of graphene and 5 parts by weight of ceramic powder, uniformly mixing, mixing the mixed powder with 10 parts by weight of organic carrier, and putting the mixture into a planetary ball mill for ball milling, wherein absolute ethyl alcohol is used as a ball milling medium, the weight ratio of the mixture to the ball milling medium is 1.5:1, the ball milling speed is 500r/min, and the time is 1.5h, so that the electronic paste composition F0 is prepared.
Example 14
An electronic paste composition F1 was prepared in the same manner as in example 13, except that 1.5 parts by weight of vanadium powder was added as an additive.
Example 15
An electronic paste composition F2 was prepared in the same manner as in example 13, except that 2.5 parts by weight of vanadium powder was added as an additive.
Example 16
An electronic paste composition F3 was prepared in the same manner as in example 13, except that 3.5 parts by weight of vanadium powder was added as an additive.
Example 17
An electronic paste composition F4 was prepared in the same manner as in example 13, except that 4.5 parts by weight of vanadium powder was added as an additive.
The resistance values at 25 deg.C, 83 deg.C, 150 deg.C and 230 deg.C of the heat-generating elements obtained from the electronic paste compositions F0-F4 of examples 13-17 were measured, and the results are shown in Table 9, and then the resistance values of the respective examples were subjected to least squares method and linear fitting to obtain temperature coefficients of resistance of examples 13-17, and the results are shown in Table 10.
TABLE 9
Watch 10
Example 18
Electronic paste compositions G1 to G13 were prepared in the same manner as in example 13 in accordance with the contents shown in table 11, 5 batches of each electronic paste were prepared, and then the electronic paste compositions of the entire batches were each printed on a ceramic substrate by a technique conventional in the art such as screen printing to form a heat-generating element, and the temperature coefficient of resistance of the heat-generating element prepared from the electronic paste compositions of the batches was obtained in the same manner as the above measurement. For each of the electronic paste compositions G1-G13, 5 lots of average temperature coefficient of resistance (average TCR) were calculated from 5 lots of temperature coefficients of resistance TCR1, TCR2, TCR3, TCR4, and TCR5, and a deviation ratio of temperature coefficient of resistance TCR (TCRn — average TCR)/average TCR (n is 1, 2, 3, 4, or 5) for each lot were calculated, and further an average deviation ratio of temperature coefficient of resistance (average value of deviation ratios of temperature coefficients of resistance for 5 lots) for the 5 lots were calculated, and the results are shown in table 12.
TABLE 11
TABLE 12
As can be seen from the above examples, excellent heating elements can be prepared by the electronic paste composition (G2-G13) of the present invention such that the average deviation of the temperature coefficients of resistance between lots is significantly lower than that of the heating elements prepared by the nickel and graphene electronic paste composition (G1) alone, showing excellent performance of uniform and low temperature coefficient of resistance.
Example 19
Weighing 89 parts by weight of cobalt powder, 11 parts by weight of graphene and 4 parts by weight of ceramic powder, uniformly mixing, mixing the mixed powder with 10 parts by weight of organic carrier, and putting the mixture into a planetary ball mill for ball milling, wherein absolute ethyl alcohol is used as a ball milling medium, the weight ratio of the mixture to the ball milling medium is 1.5:1, the ball milling speed is 500r/min, and the time is 1.5H, so that the electronic paste composition H0 is prepared.
Example 20
An electronic paste composition H1 was prepared in the same manner as in example 19, except that 1.5 parts by weight of vanadium powder was added as an additive.
Example 21
An electronic paste composition H2 was prepared in the same manner as in example 19, except that 2.5 parts by weight of vanadium powder was added as an additive.
Example 22
An electronic paste composition H3 was prepared in the same manner as in example 19, except that 3.5 parts by weight of vanadium powder was added as an additive.
Example 23
An electronic paste composition H4 was prepared in the same manner as in example 19, except that 4.5 parts by weight of vanadium powder was added as an additive.
The resistance values at 25 deg.C, 83 deg.C, 150 deg.C and 230 deg.C of the heat-generating elements obtained from the electronic paste compositions H0-H4 of examples 19-23 were measured, and the results are shown in Table 13, and then the resistance values of the respective examples were subjected to the least squares method and linear fitting to obtain temperature coefficients of resistance of examples 19-23, and the results are shown in Table 14.
Watch 13
TABLE 14
Example 24
Electronic paste compositions I1 to I13 were prepared in the same manner as in example 19, in accordance with the contents shown in table 15, 5 batches each of which was prepared, and then the entire batches of the electronic paste compositions were each printed on a ceramic substrate by a technique conventional in the art, such as screen printing, to form a heat-generating element, and the temperature coefficient of resistance of the heat-generating element prepared from the respective batches of the electronic paste compositions was obtained in the same manner as the above measurement. For each of the electronic paste compositions I1-I13, 5 lots of average temperature coefficient of resistance (average TCR) were calculated from 5 lots of temperature coefficients of resistance TCR1, TCR2, TCR3, TCR4, and TCR5, and a deviation ratio of temperature coefficient of resistance TCR (TCRn — average TCR)/average TCR (n is 1, 2, 3, 4, or 5) for each lot were calculated, and further an average deviation ratio of temperature coefficient of resistance (average value of deviation ratios of temperature coefficients of resistance for 5 lots) for the 5 lots were calculated, and the results are shown in table 16.
Watch 15
TABLE 16
As can be seen from the above examples, excellent heating elements can be prepared by the electronic paste composition (I2-I13) of the present invention such that the average deviation of the temperature coefficient of resistance between lots is significantly lower than that of the heating elements prepared by the cobalt and graphene electronic paste composition (I1) alone, showing excellent performance of uniform and low temperature coefficient of resistance.
Example 25
Weighing 89 parts by weight of chromium powder, 11 parts by weight of graphene and 4 parts by weight of porcelain powder, uniformly mixing, mixing the mixed powder with 10 parts by weight of organic carrier, and putting the mixture into a planetary ball mill for ball milling, wherein absolute ethyl alcohol is used as a ball milling medium, the weight ratio of the mixture to the ball milling medium is 1.5:1, the ball milling speed is 500r/min, and the time is 1.5h, so that the electronic paste composition J0 is prepared.
Example 26
An electronic paste composition J1 was prepared in the same manner as in example 25, except that 1.5 parts by weight of vanadium powder was added as an additive.
Example 27
An electronic paste composition J2 was prepared in the same manner as in example 25, except that 2.5 parts by weight of vanadium powder was added as an additive.
Example 28
An electronic paste composition J3 was prepared in the same manner as in example 25, except that 3.5 parts by weight of vanadium powder was added as an additive.
Example 29
An electronic paste composition J4 was prepared in the same manner as in example 25, except that 4.5 parts by weight of vanadium powder was added as an additive.
The resistance values at 25 deg.C, 83 deg.C, 150 deg.C and 230 deg.C of the heat-generating elements obtained from the electronic paste compositions J0-J4 of examples 25-29 were measured, and the results are shown in Table 17, and then the resistance values of the respective examples were subjected to the least squares method and the linear fitting to obtain the temperature coefficients of resistance of examples 25-29, and the results are shown in Table 18.
TABLE 17
Watch 18
Example 30
Electronic paste compositions K1 to K13 were prepared in the same manner as in example 25, in accordance with the contents shown in table 19, 5 batches each of which was prepared, and then the entire batches of the electronic paste compositions were each printed on a ceramic substrate by a technique conventional in the art, such as screen printing, to form a heat-generating element, and the temperature coefficient of resistance of the heat-generating element prepared from the respective batches of the electronic paste compositions was obtained in the same manner as the above measurement. For each of the electronic paste compositions K1-K13, 5 lots of average temperature coefficient of resistance (average TCR) were calculated based on 5 lots of temperature coefficients of resistance TCR1, TCR2, TCR3, TCR4 and TCR5, and the deviation ratio of temperature coefficient of resistance TCR (TCRn-average TCR)/average TCR (n is 1, 2, 3, 4 or 5) for each lot were calculated, and further the average deviation ratio of temperature coefficient of resistance (average value of deviation ratios of temperature coefficients of resistance for 5 lots) for 5 lots were calculated, as shown in Table 20.
Watch 19
Watch 20
As can be seen from the above examples, excellent heating elements can be prepared by the electronic paste composition (K2-K13) of the present invention such that the average deviation of the temperature coefficients of resistance between lots is significantly lower than that of the heating elements prepared by the chromium and graphene electronic paste composition (K1) alone, showing excellent performance of uniform and low temperature coefficient of resistance.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (11)
1. An electronic paste composition, wherein the electronic paste composition comprises a base material, a heat-generating metallic material, an additive, a porcelain powder, and an organic vehicle, and wherein the base material is selected from at least one of titanium-carbon compounds and graphene, the metallic heat-generating material is selected from at least one of tungsten, nickel, cobalt, and chromium, and the additive is selected from at least one of ruthenium, tellurium, germanium, vanadium, yttrium, and iridium.
2. The electronic paste composition according to claim 1, wherein the weight ratio of the base material to the heat-generating metal material is 0.5:9.5 to 9.5: 0.5.
3. The electronic paste composition of claim 1, the titanium carbon compound being titanium aluminum carbide, titanium silicon carbide, or a combination thereof.
4. The electronic paste composition according to claim 1 or 2, wherein the additive is contained in an amount of 0.5 to 10 wt% based on the total weight of the base material and the heat-generating metal material.
5. The electronic paste composition according to claim 1 or 2, wherein the content of the porcelain powder is 0.5 to 8% by weight based on the total weight of the base material and the heat-generating metal material.
6. The electronic paste composition according to claim 1, wherein the organic vehicle is a mixture of terpineol, ethyl cellulose, glycerol and absolute ethanol, preferably, the organic vehicle is contained in an amount of 5 to 30 wt% based on the total weight of the base material and the heat-generating metal material.
7. A method of making the electronic paste composition of any of claims 1-6, wherein the method comprises: mixing the base material, the heat-generating metal material, porcelain powder, and the additive, and then contacting the resulting mixture with the organic vehicle.
8. The method according to claim 7, wherein the contacting is performed in a ball mill, preferably with a speed of 100 and 800r/min for a time of 0.5-5 h.
9. The method according to claim 8, wherein absolute ethanol is used as a ball milling medium in the ball milling, preferably the weight ratio of the mixture to the ball milling medium is 1:1-1: 4.
10. The method as claimed in any one of claims 7 to 9, wherein the obtained electronic paste composition has a particle size of 200-500 mesh and a viscosity of 10-100 Pa-s.
11. Use of the electronic paste composition of any one of claims 1 to 6 and the electronic paste composition prepared by the method of any one of claims 7 to 10 in the preparation of a cermet heat-generating body having a low temperature coefficient of resistance.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114709006A (en) * | 2022-04-26 | 2022-07-05 | 深圳市基克纳科技有限公司 | Nickel-chromium electrothermal slurry and preparation method and application thereof |
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