CN115954133B - Resistance paste and preparation method thereof - Google Patents
Resistance paste and preparation method thereof Download PDFInfo
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- CN115954133B CN115954133B CN202310123594.4A CN202310123594A CN115954133B CN 115954133 B CN115954133 B CN 115954133B CN 202310123594 A CN202310123594 A CN 202310123594A CN 115954133 B CN115954133 B CN 115954133B
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 229910000570 Cupronickel Inorganic materials 0.000 claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 25
- 239000000956 alloy Substances 0.000 claims abstract description 25
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011521 glass Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 19
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 18
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- 239000002245 particle Substances 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 150000002910 rare earth metals Chemical class 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
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- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 claims description 2
- HDLBOHGQTWKFRG-CVBJKYQLSA-N 3-azaniumylpropylazanium;(z)-octadec-9-enoate Chemical compound NCCCN.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O HDLBOHGQTWKFRG-CVBJKYQLSA-N 0.000 claims description 2
- WWJLCYHYLZZXBE-UHFFFAOYSA-N 5-chloro-1,3-dihydroindol-2-one Chemical compound ClC1=CC=C2NC(=O)CC2=C1 WWJLCYHYLZZXBE-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- 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 2
- KGEKLUUHTZCSIP-UHFFFAOYSA-N Isobornyl acetate Natural products C1CC2(C)C(OC(=O)C)CC1C2(C)C KGEKLUUHTZCSIP-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 2
- 239000001940 [(1R,4S,6R)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl] acetate Substances 0.000 claims description 2
- -1 alcohol ester Chemical class 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 2
- SFEWMGIPBBLNJX-KTKRTIGZSA-N amino (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)ON SFEWMGIPBBLNJX-KTKRTIGZSA-N 0.000 claims description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000010445 lecithin Nutrition 0.000 claims description 2
- 239000000787 lecithin Substances 0.000 claims description 2
- 229940067606 lecithin Drugs 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 239000001739 pinus spp. Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- 229940036248 turpentine Drugs 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 229910003336 CuNi Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Non-Adjustable Resistors (AREA)
- Conductive Materials (AREA)
Abstract
The invention belongs to the technical field of electronic paste, and particularly discloses a resistor paste and a preparation method thereof. The resistance paste comprises inorganic components and organic components; the inorganic component comprises a conductive phase, a glass phase and an inorganic additive; the organic component comprises resin, an organic solvent and an organic additive, the conductive phase comprises metal boride and copper-nickel alloy, the inorganic additive comprises graphite, the ratio of the total mass of the metal boride and the copper-nickel alloy to the mass of the graphite is a, and a is more than or equal to 2 and less than or equal to 510; the mass ratio of the metal boride to the copper-nickel alloy is b, and b is more than or equal to 1. According to the invention, by controlling the ratio between the total content of the metal boride and the copper-nickel alloy and the content of graphite, the resistance adjustment of the resistance layer prepared by the resistance paste in a wider range can be realized on the basis of keeping the qualified electrical properties such as the resistance discreteness, TCR (temperature coefficient of resistance) property and the like, so that the metal boride can be applied to a resistance device in a wider resistance range.
Description
Technical Field
The invention belongs to the technical field of electronic paste, and particularly relates to a resistor paste and a preparation method thereof.
Background
Chip resistors are widely used as important electronic components in the fields of thick film circuits, hybrid integrated circuits, electronic devices, and the like. The resistance characteristics of the chip resistor are mainly determined by the resistance layer thereof, which is formed by printing a resistance paste on an insulating substrate and sintering.
The resistive paste typically includes a conductive phase and a glassy phase, the conductive phase typically employing a material such as RuO 2 、Pb 2 Ru 2 O 6.5 、Bi 2 Ru 2 O 6.5 Such noble metal materials containing Ru as a main component, resulting in high cost. At present, in order to reduce the cost, it is desired to use a metal boride such as lanthanum boride as a conductive phase material of a resistance paste, however, when the resistance value of such a resistance paste is adjusted by adjusting the contents of a conductive phase and a glass phase, since the metal boride reacts easily with other components in the paste at high temperature, a resistance layer character although final firing often occursThe resistance requirements are met, but other phenomena such as resistance discreteness and electrical characteristics such as TCR (temperature coefficient of resistance) performance cannot reach the standard, which severely limits the application of metal boride to resistor pastes in a wide range of different resistance segments. Therefore, there is an urgent need to design a new formulation of resistive paste to solve the above problems.
Disclosure of Invention
Aiming at the problems of poor resistance value discreteness, poor TCR (temperature coefficient of resistance) performance and other electrical properties of a resistance layer prepared from the metal boride-containing resistance paste related to the prior art, the invention provides the resistance paste and a preparation method thereof.
In order to achieve the above purpose, the method specifically comprises the following technical scheme:
the resistor paste comprises an inorganic component and an organic component; the inorganic component comprises a conductive phase, a glass phase and an inorganic additive; the organic component comprises resin, organic solvent and organic additive;
the conductive phase comprises metal boride and copper-nickel alloy, the inorganic additive comprises graphite, and the ratio of the total mass of the metal boride and the copper-nickel alloy to the mass of the graphite is a, and a is more than or equal to 2 and less than or equal to 510; the mass ratio of the metal boride to the copper-nickel alloy is b, and b is more than or equal to 1.
Under high-temperature sintering, the conductive phase of the resistor paste is mainly metal boride and copper-nickel alloy, oxidation-reduction reaction is easy to occur when the copper-nickel alloy and the metal boride are sintered under air to form a copper simple substance, graphite has conductivity, but the conductivity is poorer than that of the copper simple substance, so when the content of the conductive phase is less, the graphite is added to play a role in reducing resistance, when the content of the conductive phase is higher, more copper simple substance is generated, and the graphite is added to play a role in lifting resistance, namely, the effect of lifting resistance or reducing resistance can be achieved by controlling the proportion between the content of the metal boride and the copper-nickel alloy and the content of the graphite.
Experiments of the inventor of the present invention show that when the ratio a is not in the range of 2-510, the resistance of the resistance paste is discrete, and the performances such as TCR can not meet the use requirements. When the ratio a is less than 2, the graphite content is higher, and the resistance discrete performance is poor; when the ratio a > 510, the metal boride and copper nickel alloy content is excessive, so that the TCR performance is lowered.
As a preferred embodiment of the invention, the mass ratio of the metal boride to the copper-nickel alloy is b, and b is 1-250.
As a further preferred embodiment of the invention, when 1.ltoreq.b < 2.6, 2.ltoreq.a < 5.5.
As a further preferred embodiment of the present invention, 5.5.ltoreq.a.ltoreq.510 when 2.6.ltoreq.b.ltoreq.250.
Experiments of the inventor of the invention show that when b is more than or equal to 1 and less than 2.6, compared with the case that a is more than or equal to 2 and less than or equal to 5.5, if a is more than or equal to 2 or a is more than or equal to 5.5, the resistance discrete performance of the resistance slurry is reduced; when b is 2.6.ltoreq.250, the dispersion property of the resistance paste is lowered if a < 5.5, and the TCR property is deteriorated if a > 510, compared with the case where a is 5.5.ltoreq.a.ltoreq.510.
As a preferred embodiment of the present invention, the metal boride includes at least one of a rare earth metal boride and an alkaline earth metal boride.
As a further preferred embodiment of the present invention, the rare earth metal boride is a rare earth metal hexaboride and the alkaline earth metal boride is an alkaline earth metal hexaboride.
As a still further preferred embodiment of the present invention, the rare earth hexaboride is LaB 6 、CeB 6 And YB 6 At least one of (a) and (b); the alkaline earth hexaboride is CaB 6 、BaB 6 And SrB 6 At least one of them.
As a preferred embodiment of the invention, the inorganic component accounts for 40-80% by mass and the organic component accounts for 20-60% by mass, based on 100% by mass of the total mass of the resistor paste.
As a preferred embodiment of the invention, the conductive phase is 2.5-56% by mass, the glass phase is 44-97% by mass, and the inorganic additive is 0.001-10% by mass, based on 100% by mass of the total inorganic component.
As a preferred embodiment of the invention, the mass percentage of the resin is 2-15% based on 100% of the total mass percentage of the organic components, the mass percentage of the organic solvent is 75-95%, and the mass percentage of the organic additive is 0.1-18%.
As a preferred embodiment of the present invention, the glass phase comprises the following components in percentage by mass, based on 100% by mass of the total glass phase: siO (SiO) 2 22-65％，Al 2 O 3 2-25％，B 2 O 3 5-40％，CaO 2-15％，Ta 2 O 5 0-50％，MgO 0-10％，SrO 0-10％，TiO 0-10％，ZnO 0-10％，Na 2 O 0-10％，K 2 O 0-10％。
As a preferred embodiment of the present invention, the inorganic additive further comprises Nb 2 O 5 、Ta 2 O 5 At least one of TiO and Si.
As a preferred embodiment of the present invention, the average particle diameter of the metal boride is in the range of 0.1 to 10. Mu.m; the average grain diameter of the copper-nickel alloy ranges from 0.1 to 10 mu m; the average particle size of the glass phase ranges from 0.5 to 2 mu m; the average particle diameter of the inorganic additive ranges from 0.1 to 5 mu m.
As a preferred embodiment of the present invention, the resin includes at least one of methyl cellulose, ethyl cellulose, acrylic resin, epoxy resin, alkyd resin, terpene resin, and modified rosin.
As a preferred embodiment of the present invention, the organic solvent includes at least one of terpineol, butyl carbitol acetate, diethylene glycol dibutyl ether, turpentine, isobornyl acetate, dibutyl phthalate, and alcohol ester twelve.
As a preferred embodiment of the present invention, the organic additive includes at least one of sodium dodecyl sulfate, methyl amyl alcohol, aminopropylamine dioleate, oil amino oleate, lecithin.
In the resistor paste, the glass phase mainly bonds the conductive phases together to form a conductive path, maintains the integrity of the thick film resistor, and plays an important role in bonding with a substrate; the inorganic additives mainly function to adjust electrical properties such as TCR, electrostatic properties (ESD), etc.; the organic component acts as a dispersion medium and affects mainly the application properties of the slurry, especially the rheological properties.
A preparation method of the resistor paste comprises the following steps:
(1) Heating and dissolving resin in an organic solvent, adding an organic additive, filtering and cooling to obtain an organic carrier;
(2) Mixing and dispersing the conductive phase, the glass phase and the inorganic additive to obtain inorganic mixed powder;
(3) And adding the inorganic mixed powder into the organic carrier, and uniformly dispersing to obtain the resistor paste.
As a preferred embodiment of the present invention, in the step (1), the dissolution temperature is 60 to 120 ℃.
As a further preferred embodiment of the present invention, in step (1), the temperature of dissolution is 80 ℃.
As a preferred embodiment of the present invention, in the step (1), the dissolution is performed under stirring at a rate of 10 to 480 rpm.
As a further preferred embodiment of the present invention, in step (1), the dissolution is carried out under stirring at a rate of 280 rpm.
In the step (3), the dispersing and homogenizing method specifically comprises the following steps: premixing under stirring at 60-720 r/min, and dispersing thoroughly and uniformly by a three-roller mill.
Compared with the prior art, the invention has the following beneficial effects: the conductive phase material in the resistance paste comprises metal boride and copper-nickel alloy, the inorganic additive contains graphite, and the resistance adjustment of the resistance layer prepared by the resistance paste in a wider range can be realized on the basis of keeping the qualified electrical properties such as resistance discreteness, TCR (temperature coefficient) performance and the like by controlling the proportion between the total content of the metal boride and the copper-nickel alloy and the content of the graphite, so that the metal boride can be applied to resistance devices in a wider range of resistance.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described by means of specific examples.
Size data for the conductive phases, glass frit, inorganic additives of examples and comparative examples:
(1) The average particle diameter of the metal boride was 0.1 to 10. Mu.m, and the average particle diameters in examples and comparative examples were 1.0. Mu.m;
(2) The average particle diameter of the copper nickel (CuNi) alloy powder is 0.1 to 10 μm, and the average particle diameters in examples and comparative examples are 0.5 μm;
(3) The average particle size of the glass phase powder was 0.5 to 2. Mu.m, and the average particle size in examples and comparative examples was 1.5. Mu.m;
(4) The average particle size of the inorganic additive was 0.1 to 5. Mu.m, and the average particle size in examples and comparative examples was 2. Mu.m.
Examples and comparative examples
The types of glass phases in examples and comparative examples are shown in table 1.
Table 1 the compositions of the glass phases in the examples and comparative examples
According to the raw material formulation in table 2, the preparation method of the resistor paste of examples and comparative examples comprises the following steps:
(1) Heating to 80deg.C, uniformly dissolving resin in organic solvent at 280 rpm with straight blade paddle, adding organic additive, filtering, and cooling to room temperature to obtain viscous gel organic carrier;
(2) Premixing and dispersing a conductive phase, a glass phase and an inorganic additive to obtain inorganic mixed powder;
(3) Adding the inorganic mixed powder into an organic carrier, firstly stirring, taking 580 r/min through a straight blade paddle for premixing, and then fully and uniformly dispersing through a three-roller mill to finally obtain the resistor slurry.
(1) Performance characterization method
(1-1) the content of the metal boride and the copper-nickel alloy powder can be obtained by testing by an X-ray photoelectron spectroscopy (XRF) method.
(2-2) detection of graphite content:
A. the organic phase and the inorganic phase of the resistive paste are separated: adding a certain amount of resistance slurry into acetone, stirring until the resistance slurry is dissolved in the acetone (gel-like substance is not present), standing for 12-24h, layering the slurry, removing the upper organic phase, repeating for more than 6 times, removing the upper organic phase, and drying at 150 ℃ to obtain the lower inorganic phase powder.
B. The quantitative analysis method of the separated inorganic phase comprises the following steps: the carbon content of the inorganic phase powder can be measured by a carbon-sulfur instrument, namely the content of graphite in the resistor paste.
Wherein, whether the separation of the organic in the inorganic phase is complete is identified: DSC test is carried out on the dried powder, whether an exothermic peak exists at 600 ℃ or not is observed in the graph, if the exothermic peak exists, the organic phase exists, and if the exothermic peak does not exist, the organic phase is completely separated.
(2) Performance index and test method
(2-1) application of resistive paste preparation on chip resistor sample preparation:
the size of the resistance layer of 1206 sheet resistor specification (effective size 1mm x 1.32mm, sintered film thickness 6-12 μm) is used as test sample, the resistance slurries of the examples and the comparative examples are printed on an alumina substrate by a screen printing process, and the test sample is obtained after sintering in an air atmosphere of 650-950 ℃ (the samples of the examples and the comparative examples are all selected to be performed at 820 ℃), and the number of the test samples is n.
(2-2) resistance R and resistance discrete RSD test:
the resistance Ri of each test sample obtained above was tested by using a resistance tester, and the average resistance of all test samples was calculated
Calculating the discrete coefficient of resistance value by the formula +.>
And when RSD is less than or equal to 6%, the product is qualified. Wherein n of the test samples of examples and comparative examples is 500.
(2-3) TCR testing:
the samples were tested for resistance and TCR calculated at constant temperature conditions of 125℃and 25℃and-55℃for 10min, respectively.
Wherein, when calculating low temperature (cold) TCR (CTCR), t= -55 ℃; when calculating the high temperature (hot) TCR (HTCR), t=125 ℃; when CTCR and HTCR are within + -100 ppm/DEG C, the performance of the resistive device meets the standard.
Table 2 examples and comparative examples resistor paste formulations
Table 3 resistor performance results for example and comparative resistor slurries
Wherein, in Table 3, the value of a is the ratio of the total mass of the metal boride and the copper-nickel alloy to the mass of graphite; the value b is the mass ratio of the metal boride to the copper-nickel alloy.
As can be seen from examples 1-11 and comparative examples 1-2, when a is 2.ltoreq.a.ltoreq.510 and b.ltoreq.1, the resistance value dispersion and TCR performance of the resistor prepared from the resistor paste reach the standards; when the ratio a is not in the range of 2-510, the resistance value obtained by the resistance paste is discrete, and the performances such as TCR and the like can not meet the use requirements; when the ratio a is less than 2, the graphite content is higher, and the resistance discrete performance is poor; when the ratio a > 510, the metal boride and copper nickel alloy content is excessive, so that the TCR performance is lowered.
As can be seen from examples 1-3, 12-14, examples 1-3 have b values falling within the interval 2.6-250 and a values falling within the range 2-5.5; whereas examples 12-14 had b values in the range of 1-2.6 and a values in the range of 2-5.5, examples 12-14 produced resistors having better discrete resistance values than the resistors of examples 1-3, examples 12-14.
From examples 5, 8, 10, 15-17, examples 5, 8, 10 have b values falling within the range of 2.6-250 and a values in the range of 5.5-510; examples 15-17 have b values in the range of 1-2.6 and a values in the range of 5.5-510, and examples 5, 8, 10 provide resistors having better resistance dispersion properties than the resistor pastes of examples 15-17, examples 5, 8, 10.
As is clear from examples 4, 18-22, the RSD value of the resistor made of the resistive paste was decreased and then increased when the b value was varied and the b value was within the range of 5.5-250.
As can be seen from examples 23 to 31, when 2.ltoreq.a.ltoreq.510 and b.ltoreq.1, the metal boride includes at least one of a rare earth metal boride and an alkaline earth metal boride, and the rare earth metal hexaboride may also be CeB 6 And YB 6 At least one of the alkaline earth hexaboride may be CaB 6 、BaB 6 And SrB 6 At least one of glass phase, resin, solvent and organic additive, and their contents, and resistance slurries with different resistance sectionsThe obtained TCR and RSD reach the standard. Therefore, the invention can realize the adjustment of the resistance value of the resistance layer prepared by the resistance paste in a wider range on the basis of keeping the qualified electrical properties such as the resistance value discreteness, TCR performance and the like.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The resistor paste is characterized by comprising an inorganic component and an organic component; the inorganic component comprises a conductive phase, a glass phase and an inorganic additive; the organic component comprises resin, organic solvent and organic additive;
the conductive phase comprises metal boride and copper-nickel alloy, the inorganic additive comprises graphite, and the ratio of the total mass of the metal boride and the copper-nickel alloy to the mass of the graphite is a, and a is more than or equal to 2 and less than or equal to 510; the mass ratio of the metal boride to the copper-nickel alloy is b, and b is more than or equal to 1.
2. The resistor paste of claim 1 wherein the mass ratio of metal boride to copper nickel alloy is b and b is 1-250.
3. The resistive paste of claim 1, wherein 2.ltoreq.a < 5.5 when 1.ltoreq.b < 2.6, or 5.5.ltoreq.a.ltoreq.510 when 2.6.ltoreq.b.ltoreq.250.
4. The resistive paste of claim 1, comprising at least one of the following (a) - (E):
(A) The metal boride comprises at least one of rare earth metal boride and alkaline earth metal boride;
(B) The inorganic additive further comprises Nb 2 O 5 、Ta 2 O 5 At least one of TiO, si;
(C) The resin comprises at least one of methyl cellulose, ethyl cellulose, acrylic resin, epoxy resin, alkyd resin, terpene resin and modified rosin;
(D) The organic solvent comprises at least one of terpineol, butyl carbitol acetate, diethylene glycol dibutyl ether, turpentine, isobornyl acetate, dibutyl phthalate and alcohol ester twelve;
(E) The organic additive comprises at least one of sodium dodecyl sulfate, methyl amyl alcohol, aminopropylamine dioleate, oil amino oleate and lecithin.
5. The resistor paste of claim 4, wherein the rare earth boride is a rare earth hexaboride and the alkaline earth boride is an alkaline earth hexaboride; the rare earth hexaboride is LaB 6 、CeB 6 And YB 6 At least one of (a) and (b); the alkaline earth hexaboride is CaB 6 、BaB 6 And SrB 6 At least one of them.
6. The resistive paste according to claim 1, wherein the inorganic component is 40 to 80% by mass and the organic component is 20 to 60% by mass based on 100% by mass of the total resistive paste.
7. The resistive paste according to claim 1, wherein the conductive phase is 2.5 to 56% by mass, the glass phase is 44 to 97% by mass, and the inorganic additive is 0.001 to 10% by mass, based on 100% by mass of the total inorganic components;
the mass percentage of the resin is 2-15 percent, the mass percentage of the organic solvent is 75-95 percent and the mass percentage of the organic additive is 0.1-18 percent based on 100 percent of the total mass percentage of the organic components;
the glass phase comprises the following components in percentage by mass based on 100% of the total mass of the glass phase: siO (SiO) 2 22-65％，Al 2 O 3 2-25％，B 2 O 3 5-40％，CaO 2-15％，Ta 2 O 5 0-50％，MgO0-10％，SrO 0-10％，TiO 0-10％，ZnO 0-10％，Na 2 O 0-10％，K 2 O 0-10％。
8. The resistor paste of claim 1, wherein the metal boride has an average particle size in the range of 0.1 to 10 μm; the average grain diameter of the copper-nickel alloy ranges from 0.1 to 10 mu m; the average particle size of the glass ranges from 0.5 to 2 mu m; the average particle diameter of the inorganic additive ranges from 0.1 to 5 mu m.
9. A method of preparing a resistive paste according to any one of claims 1 to 8, comprising the steps of:
(1) Heating and dissolving resin in an organic solvent, adding an organic additive, filtering and cooling to obtain an organic carrier;
(2) Premixing and dispersing a conductive phase, a glass phase and an inorganic additive to obtain inorganic mixed powder;
(3) And adding the inorganic mixed powder into the organic carrier, and uniformly dispersing to obtain the resistor paste.
10. The method of preparing a resistive paste according to claim 9, wherein in step (1), the dissolution temperature is 60-120 ℃; in the step (1), the dissolution is carried out under the condition of stirring, and the stirring speed is 10-480 r/min; in the step (3), the uniform dispersion specifically comprises the following steps: premixing under stirring at 60-720 r/min, and dispersing thoroughly and uniformly by a three-roller mill.
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| CN115954133B true CN115954133B (en) | 2023-07-14 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225468A (en) * | 1978-08-16 | 1980-09-30 | E. I. Du Pont De Nemours And Company | Temperature coefficient of resistance modifiers for thick film resistors |
| US4512917A (en) * | 1983-08-22 | 1985-04-23 | E. I. Du Pont De Nemours And Company | Hexaboride resistor composition |
| US4597897A (en) * | 1985-06-24 | 1986-07-01 | E. I. Du Pont De Nemours And Company | Hexaboride resistor composition |
| US4985176A (en) * | 1987-12-04 | 1991-01-15 | Murata Manufacturing Co., Ltd. | Resistive paste |
| WO2020139530A1 (en) * | 2018-12-28 | 2020-07-02 | Heraeus Precious Metals North America Conshohocken Llc | Conductive pastes for pattern transfer printing |
-
2023
- 2023-02-16 CN CN202310123594.4A patent/CN115954133B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225468A (en) * | 1978-08-16 | 1980-09-30 | E. I. Du Pont De Nemours And Company | Temperature coefficient of resistance modifiers for thick film resistors |
| US4512917A (en) * | 1983-08-22 | 1985-04-23 | E. I. Du Pont De Nemours And Company | Hexaboride resistor composition |
| US4597897A (en) * | 1985-06-24 | 1986-07-01 | E. I. Du Pont De Nemours And Company | Hexaboride resistor composition |
| US4985176A (en) * | 1987-12-04 | 1991-01-15 | Murata Manufacturing Co., Ltd. | Resistive paste |
| WO2020139530A1 (en) * | 2018-12-28 | 2020-07-02 | Heraeus Precious Metals North America Conshohocken Llc | Conductive pastes for pattern transfer printing |
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| CN115954133A (en) | 2023-04-11 |
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