CN114512260A - Lead-free copper paste suitable for medium-temperature sintering of PZT sensor and preparation method thereof - Google Patents
Lead-free copper paste suitable for medium-temperature sintering of PZT sensor and preparation method thereof Download PDFInfo
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- CN114512260A CN114512260A CN202210152774.0A CN202210152774A CN114512260A CN 114512260 A CN114512260 A CN 114512260A CN 202210152774 A CN202210152774 A CN 202210152774A CN 114512260 A CN114512260 A CN 114512260A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 52
- 239000010949 copper Substances 0.000 title claims abstract description 52
- 238000005245 sintering Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 83
- 239000011521 glass Substances 0.000 claims abstract description 75
- 239000002904 solvent Substances 0.000 claims abstract description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 12
- 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 abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 12
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 11
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002952 polymeric resin Substances 0.000 claims abstract description 6
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052810 boron oxide Inorganic materials 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 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
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 229940116411 terpineol Drugs 0.000 claims description 4
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 claims description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- H01B1/14—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
- 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
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Conductive Materials (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of PZT sensors, in particular to a medium-temperature sintering lead-free copper paste suitable for a PZT sensor and a preparation method thereof, wherein the lead-free copper paste comprises the following components in parts by mass: 70 to 80 parts of copper powder, 1 to 5 parts of lead-free glass, 1 to 5 parts of inorganic additive and 15 to 25 parts of organic carrier; the copper powder is one or two of superfine spherical powder and flaky micro powder; the lead-free glass is a mixture consisting of glass powder A and glass powder B, the softening point of the glass powder A is between 480 ℃ and 520 ℃, and the softening point of the glass powder B is between 520 ℃ and 560 ℃; the inorganic additive is one or two of electronic grade bismuth oxide powder or superfine zirconium dioxide; the organic carrier comprises the following components in parts by mass: 70-80 parts of solvent, 10-20 parts of ethyl cellulose, 5-10 parts of high polymer resin material and 1-5 parts of flatting agent; according to the invention, on the premise of ensuring the conductivity, silver powder is replaced by copper powder, and the problem of the binding force between the softened medium-temperature sintered glass and the ceramic substrate is solved.
Description
Technical Field
The invention relates to the technical field of PZT sensors, in particular to a medium-temperature sintering lead-free copper paste suitable for a PZT sensor and a preparation method thereof.
Background
With the development of the electronic industry, the demand for sensors is increasing day by day, the production cost of products is further reduced, the profit of enterprises is gradually reduced, and the pressure of the industry on the product cost is also increasing.
The production process of the PZT sensor industry is mainly as follows: firstly, preparing a ceramic chip; secondly, surface metallization (printing and drying of an electrode layer, and sintering at 850 ℃ in 750-; and high voltage polarization. The above process shows that: first, the surface metallization sintering temperature is between 750 and 850 ℃, which is not advantageous in terms of energy consumption, time and other costs, and particularly for some special sensors, at this temperature, high temperature may have adverse effects on the electrical properties. If the sintering temperature of the electrode layer can be reduced (600-700 ℃ in nitrogen atmosphere), the production efficiency is greatly improved, the enterprise cost (working hours, energy consumption of a sintering furnace and the like) is reduced, and the destructive influence on the piezoelectric ceramic body structure is further reduced. Secondly, precious metal silver is adopted for surface metallization at present, the total cost of the sensor is more than 60%, if the precious metal silver can be replaced by base metal copper, the cost is greatly reduced (the price of copper powder is approximately equal to 1/5), and the method has extremely high economic value for low-cost generalization of enterprises and the whole industry.
In this respect, copper powder has been used to replace silver powder in the industry, and the prior cases of low-temperature sintering have appeared, but two new problems have appeared in general:
the silver powder is replaced by copper powder, so that the conductivity of the electrode can be influenced, and further, the polarization is insufficient in the later polarization process, so that the performance of the PZT sensor is influenced;
the reduction of the sintering temperature has an effect on the formation of a glass softening point which is difficult to control (unless lead-containing glass is used, but this cannot meet the RoHS requirement), and not only the bonding force between the electrode layer and the ceramic substrate is affected, but also the uniformity of the distribution of the electrode layer is affected, thereby further affecting the performance of the PZT sensor.
Disclosure of Invention
The invention provides a lead-free copper paste suitable for medium-temperature sintering of a PZT sensor and a preparation method thereof, which replace silver powder with copper powder on the premise of ensuring the conductivity and simultaneously solve the problem of the bonding force between softened medium-temperature sintered glass and a ceramic substrate.
In order to achieve the purpose, the invention provides the following technical scheme: the lead-free copper paste suitable for medium-temperature sintering of the PZT sensor comprises the following components in parts by mass: 70 to 80 parts of copper powder, 1 to 5 parts of lead-free glass, 1 to 5 parts of inorganic additive and 15 to 25 parts of organic carrier; the copper powder is one or two of superfine spherical powder and flaky micro powder; the flake micro powder accounts for 10-30% of the copper powder, and the superfine spherical micro powder accounts for 70-90% of the copper powder; the lead-free glass is a mixture consisting of glass powder A and glass powder B, the softening point of the glass powder A is between 480 and 520 ℃, and the softening point of the glass powder B is between 520 and 560 ℃; the inorganic additive is one or two of electronic grade bismuth oxide powder or superfine zirconium dioxide; the organic carrier comprises the following components in parts by mass: 70-80 parts of solvent, 10-20 parts of ethyl cellulose, 5-10 parts of high polymer resin material and 1-5 parts of flatting agent; the lead-free copper paste pre-dispersion method comprises the following steps: weighing 90 parts of copper powder, 5 parts of carrier and 5 parts of dispersing agent according to a proportion, fully stirring or fully dispersing in the dispersing agent, and then uniformly rolling by using a three-roll mill until the fineness is less than or equal to 8 mu m.
Preferably, the glass powder A is lead-free glass powder and comprises the following components in parts by weight: 60 to 70 parts of bismuth oxide, 10 to 15 parts of boron oxide, 5 to 10 parts of silicon oxide, 15 to 25 parts of zinc oxide, 1 to 5 parts of aluminum oxide, 1 to 3 parts of lithium carbonate and 1 to 3 parts of zirconium dioxide.
Preferably, the glass powder B is lead-free glass powder and comprises the following components in parts by mass: 50 to 60 parts of bismuth oxide, 15 to 20 parts of boron oxide, 10 to 15 parts of silicon oxide, 10 to 20 parts of zinc oxide, 1 to 5 parts of barium carbonate, 1 to 3 parts of titanium dioxide and 1 to 3 parts of sodium carbonate.
Preferably, the dispersant adopts one or more of EFKA-4047, 4050, 4080 or BYKJ-110, 164.
Preferably, the solvent comprises one or more of terpineol, diethylene glycol butyl ether, butyl carbitol acetate, carbonate type environment-friendly solvent and dipropylene glycol methyl ether acetate.
Preferably, the ethylcellulose type number comprises one or more of 45, 100, 200.
Preferably, the polymer resin material comprises one or more of phenolic resin, modified epoxy resin, alkyd resin or maleic resin.
Preferably, one or two of ByK-300, 361N and 333 is/are adopted as the leveling agent.
Preferably, the preparation method comprises the following steps:
step 1, weighing copper powder, an organic carrier and a dispersing agent according to a weight ratio, uniformly mixing, and further uniformly rolling under a three-roll mill to obtain a copper paste intermediate with the fineness of less than or equal to 8 microns for later use;
step 2, weighing one or more of the inorganic additives according to the weight ratio, uniformly mixing, pouring into cold water for quenching to obtain solid glass particles, putting the solid glass particles into a planetary ball mill, adding water for ball milling for 14-20 hours, drying, and crushing to obtain glass powder A and glass powder B for later use;
step 3, weighing the solvent, the ethyl cellulose, the resin, the flatting agent or the dispersing agent and the wetting agent according to the weight ratio, heating and stirring the mixture for 1 to 2 hours at the temperature of between 50 and 60 ℃, and uniformly mixing the mixture to obtain an organic carrier for later use;
and 4, weighing the silver powder, the glass powder, the inorganic additive, the carrier 1 and the carrier 2 according to the weight ratio, fully stirring and mixing, and further uniformly dispersing in a three-roll grinder, wherein the fineness of the obtained lead-free copper slurry is less than or equal to 6 microns.
Preferably, in the step 2, the glass powder A is obtained by smelting for 30-60 min at the temperature of 1000-1200 ℃; the glass powder B is obtained by smelting for 60-90 min at 1200-1400 ℃.
The invention has the beneficial effects that:
the preparation process of the lead-free copper paste is simple and easy to realize;
the prepared lead-free copper paste can well permeate into a PZT base body in the medium temperature (600-700 ℃ in nitrogen) sintering process by matching the superfine spherical micro powder and the flaky micro powder, and can form a compact film layer to realize good conductivity;
the copper powder is pre-dispersed, so that the stability and uniformity of the distribution of the copper powder in the later lead-free copper paste are facilitated, and the performance is greatly improved compared with that of the conventional paste preparation method;
the prepared glass powder A has good melting effect in the sintering process under the medium temperature condition (600-700 ℃ in nitrogen atmosphere), and can permeate into the PZT porcelain body, so that the electrode layer and the PZT substrate are tightly combined, and the product adhesion is ensured;
the prepared glass powder B has good melting effect in the sintering process under the medium temperature condition (600-700 ℃ C., nitrogen atmosphere), wherein the added Li element has a certain promotion effect on the performance of the PZT ceramic, and simultaneously, the Li element is inserted between the conducting layers to play a role in protecting the conducting layers, thereby providing good guarantee for the reliability of later use of the product;
the glass powder and other materials adopted by the prepared lead-free copper paste are free of lead, and both accord with RoHS regulations, so that the lead-free and environment-friendly requirements of customers on the electronic paste are met;
the prepared lead-free copper paste is low in cost and only accounts for 20-30% of the traditional silver paste;
compared with the traditional silver paste, the performance of the prepared lead-free copper paste has no obvious difference and can be completely replaced.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the 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.
The lead-free copper paste suitable for medium-temperature sintering of the PZT sensor comprises the following components in parts by mass: 70 to 80 parts of copper powder, 1 to 5 parts of glass powder, 1 to 5 parts of inorganic additive and 15 to 25 parts of organic carrier.
The copper powder in the lead-free copper paste is one or two of superfine spherical powder and flaky micro powder, the particle size is selected to meet the requirement that the D50 of the superfine spherical powder is 0.2-0.8 mu m, and the D90 is not more than 1 mu m, so that the silver powder has a good melting state during medium-temperature sintering; the flake micro powder is selected to meet the requirement that D50 is between 1 and 4 mu m, D90 is not more than 5 mu m, and is used for filling sintering holes of the superfine spherical micro powder so as to ensure the continuity and compactness of the sintered electrode layer, in addition, the superfine spherical micro powder accounts for 70 to 90 percent of the total proportion of the copper powder, and the superfine spherical micro powder can be adjusted in the range according to the process requirements.
The copper powder in the lead-free copper slurry needs to be dispersed in advance, namely pre-dispersion, and the dispersing agent adopts one or more of EFKA-4047, 4050, 4080 or BYKJ-110 and 164, and the dispersing agent has a good effect on the dispersion of the high-content copper powder in the slurry, so that the stability and the consistency of the copper slurry in the later period are ensured.
The dispersion method of the lead-free copper paste comprises the following steps: weighing 90 parts of copper powder, 5 parts of carrier and 5 parts of dispersing agent according to the mass parts, fully stirring or fully dispersing in the dispersing agent, and then uniformly rolling by using a three-roll mill until the fineness is less than or equal to 8 microns;
the lead-free glass in the lead-free copper paste is a mixture consisting of glass powder A and glass powder B,
the glass powder A is lead-free glass powder and comprises the following components in parts by mass: 60 to 70 parts of bismuth oxide, 10 to 15 parts of boron oxide, 5 to 10 parts of silicon oxide, 15 to 25 parts of zinc oxide, 1 to 5 parts of aluminum oxide, 1 to 3 parts of lithium carbonate and 1 to 3 parts of zirconium dioxide.
The glass powder B is lead-free glass powder and comprises the following components in parts by mass: 50 to 60 parts of bismuth oxide, 15 to 20 parts of boron oxide, 10 to 15 parts of silicon oxide, 10 to 20 parts of zinc oxide, 1 to 5 parts of barium carbonate, 1 to 3 parts of titanium dioxide and 1 to 3 parts of sodium carbonate.
The particle size of the glass powder in the lead-free copper paste is in accordance with that D50 is between 1 and 3 mu m, D90 is not more than 5 mu m so as to obtain better permeation effect, the softening point of the glass powder A is between 480 and 520 ℃, and the softening point of the glass powder B is between 520 and 560 ℃. The glass powder A mainly plays a role in enhancing adhesion, and the glass powder B plays a role in enhancing the strength and the welding resistance of the film layer, so that the bad effect generated after silver is replaced by copper is solved.
The inorganic additive in the lead-free copper paste is one or two of electronic grade bismuth oxide powder or superfine zirconium dioxide, and the particle size of the inorganic additive is consistent with that D50 is not more than 3 mu m and D90 is not more than 10 mu m.
The lead-free copper paste comprises the following organic carriers in parts by mass: 70 to 80 parts of solvent, 10 to 20 parts of ethyl cellulose, 5 to 10 parts of high polymer resin material and 1 to 5 parts of flatting agent.
The solvent comprises one or more of terpineol, diethylene glycol butyl ether, butyl carbitol acetate, carbonate environment-friendly solvent and dipropylene glycol methyl ether acetate, the terpineol can be used as a main solvent in the process with higher requirement on fluidity, the diethylene glycol butyl ether can be used as a main solvent in the process with higher requirement on thixotropy, and other solvents are used for adjusting the proportion by adjusting the effects of solubility, volatility and the like.
Wherein, the ethyl cellulose type includes one or more of 45, 100 and 200, and the same type of American Dow STD series can be adopted for the higher performance requirement.
Wherein the high molecular resin material comprises one or more of phenolic resin, modified epoxy resin, alkyd resin or maleic resin.
One or two of BYK-300, 361N and 333 is/are adopted as the leveling agent. Because the proportion of the silver powder and other solid powder in the silver paste is 60-70%, the copper powder and the solid powder account for 75-85% in the invention, and the fluidity of the whole paste is greatly influenced, the adoption of the flatting agents greatly helps the construction such as later printing, and if the flatting agent is not used, the later use is greatly problematic. In addition, in order to facilitate the adjustment of viscosity of the lead-free copper paste in the later period, the organic carrier can adjust the components into two groups,
carrier 1 (high viscosity): 70 to 80 parts of solvent, 15 to 20 parts of ethyl cellulose and 5 to 10 parts of resin;
carrier 2 (low viscosity): 80 to 90 parts of solvent, 5 to 10 parts of ethyl cellulose, 3 to 10 parts of macromolecular resin and 1 to 5 parts of flatting agent.
The preparation method of the lead-free copper paste suitable for the medium-temperature sintering process of the PZT sensor comprises the following steps:
step 1, weighing copper powder (superfine spherical powder and flaky micro powder), an organic carrier and a dispersing agent according to a weight ratio, uniformly mixing, and further uniformly rolling under a three-roll mill to obtain a copper paste intermediate with the fineness of less than or equal to 8 microns for later use.
Step 2, one or more of the inorganic additives contained in the two glasses are respectively weighed according to the weight ratio, the two glasses are uniformly mixed, then the mixture is smelted for a certain time (30-60 min; 60-90 min) at a certain temperature (1000-1200 ℃ of glass powder A; 1200-1400 ℃ of glass powder B), the mixture is poured into cold water for quenching to obtain solid glass particles, the solid glass particles are placed into a planetary ball mill and then are added with water for ball milling for 14-20 hours, and the solid glass particles are dried and crushed to obtain the glass powder A and the glass powder B for later use.
And 3, weighing the solvent, the ethyl cellulose, the resin, the flatting agent or the dispersing agent and the wetting agent according to the weight ratio, heating and stirring the mixture for 1 to 2 hours at the temperature of between 50 and 60 ℃, and uniformly mixing the mixture to obtain the organic carrier for later use.
And 4, weighing the silver powder, the glass powder, the inorganic additive, the carrier 1 and the carrier 2 according to the weight ratio, fully stirring and mixing, and further uniformly dispersing in a three-roll grinder, wherein the fineness of the obtained lead-free copper slurry is less than or equal to 6 microns.
In practical application, the formula can be realized by adopting the following formula proportion:
1. the formula proportion of the glass powder is as follows:
2. the formula proportion of the organic carrier is as follows:
carrier 1:
carrier 2:
3. the proportion of the formula of the lead-free copper paste (taking the copper content of 80% as an example, spherical: flaky):
| raw materials | Copper paste 1# (7:3) | Copper paste 2# (9:1) | Copper paste 3# (3:7) |
| Superfine spherical micro powder | 56 | 72 | 24 |
| Flake micro powder | 24 | 8 | 56 |
| Glass powder | 2.5 | 2.5 | 2.5 |
| Bismuth oxide | 0.5 | 0.5 | 0.5 |
| Zirconium oxide | 0.5 | 0.5 | 0.5 |
| Carrier 1 | 6.5 | 4.5 | 8.5 |
| Carrier 2 | 10 | 12 | 8 |
According to the formula, the following steps are respectively carried out:
step 1: preparing glass powder: the glass powder is prepared by weighing the raw materials according to the weight ratio, uniformly mixing, and then respectively carrying out smelting, water quenching, ball milling, drying and crushing according to the requirements in the invention.
Step 2: preparing an organic carrier: the raw materials are weighed according to the proportion and are respectively dissolved according to the requirements in the invention content to obtain the organic carrier for later use.
And step 3: weighing various raw materials according to the formula of the copper paste and the formula of the glass paste respectively, stirring uniformly, and then rolling uniformly in a three-roll grinding machine to obtain the copper paste.
And 4, step 4: taking a plurality of PZT sensor substrates, printing copper paste, and drying at 150 ℃ for 5-10 min;
and 5: and sintering the dried substrate at 600 ℃ (nitrogen atmosphere) to obtain the PZT sensor.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The lead-free copper paste suitable for medium-temperature sintering of the PZT sensor is characterized by comprising the following components in parts by weight: 70 to 80 parts of copper powder, 1 to 5 parts of lead-free glass, 1 to 5 parts of inorganic additive and 15 to 25 parts of organic carrier;
the copper powder is one or two of superfine spherical powder and flaky micro powder; the flake micro powder accounts for 10-30% of the copper powder, and the superfine spherical micro powder accounts for 70-90% of the copper powder;
the lead-free glass is a mixture consisting of glass powder A and glass powder B, wherein the softening point of the glass powder A is between 480 ℃ and 520 ℃, and the softening point of the glass powder B is between 520 ℃ and 560 ℃;
the inorganic additive is one or two of electronic grade bismuth oxide powder or superfine zirconium dioxide;
the organic carrier comprises the following components in parts by weight: 70-80 parts of solvent, 10-20 parts of ethyl cellulose, 5-10 parts of high polymer resin material and 1-5 parts of flatting agent;
the lead-free copper paste pre-dispersion method comprises the following steps: weighing 90 parts of copper powder, 5 parts of carrier and 5 parts of dispersing agent according to a proportion, fully stirring or fully dispersing in the dispersing agent, and then uniformly rolling by using a three-roll mill until the fineness is less than or equal to 8 mu m.
2. The lead-free copper paste suitable for medium-temperature sintering of PZT sensors according to claim 1, wherein: the glass powder A is lead-free glass powder and comprises the following components in parts by mass: 60 to 70 parts of bismuth oxide, 10 to 15 parts of boron oxide, 5 to 10 parts of silicon oxide, 15 to 25 parts of zinc oxide, 1 to 5 parts of aluminum oxide, 1 to 3 parts of lithium carbonate and 1 to 3 parts of zirconium dioxide.
3. The lead-free copper paste suitable for medium-temperature sintering of PZT sensors according to claim 1, wherein: the glass powder B is lead-free glass powder and comprises the following components in parts by mass: 50 to 60 parts of bismuth oxide, 15 to 20 parts of boron oxide, 10 to 15 parts of silicon oxide, 10 to 20 parts of zinc oxide, 1 to 5 parts of barium carbonate, 1 to 3 parts of titanium dioxide and 1 to 3 parts of sodium carbonate.
4. The lead-free copper paste suitable for medium-temperature sintering of PZT sensors according to claim 1, wherein: the dispersing agent adopts one or more of EFKA-4047, 4050, 4080 or BYKJ-110 and 164.
5. The lead-free copper paste suitable for medium-temperature sintering of PZT sensors according to claim 1, wherein: the solvent comprises one or more of terpineol, diethylene glycol butyl ether, butyl carbitol acetate, a carbonate environment-friendly solvent and dipropylene glycol methyl ether acetate.
6. The lead-free copper paste suitable for medium-temperature sintering of PZT sensors according to claim 1, wherein: the ethyl cellulose type number includes one or more of 45, 100, 200.
7. The lead-free copper paste suitable for medium-temperature sintering of PZT sensors according to claim 1, wherein: the high polymer resin material comprises one or more of phenolic resin, modified epoxy resin, alkyd resin or maleic resin.
8. The lead-free copper paste suitable for medium-temperature sintering of PZT sensors according to claim 1, wherein: one or two of BYK-300, 361N and 333 is/are adopted as the leveling agent.
9. The lead-free copper paste suitable for medium-temperature sintering of PZT sensors as claimed in claim 1, wherein the preparation method comprises the following steps:
step 1, weighing copper powder, an organic carrier and a dispersing agent according to a weight ratio, uniformly mixing, and further uniformly rolling under a three-roll mill to obtain a copper paste intermediate with the fineness of less than or equal to 8 microns for later use;
step 2, weighing one or more of the inorganic additives according to the weight ratio, uniformly mixing, pouring into cold water for quenching to obtain solid glass particles, putting the solid glass particles into a planetary ball mill, adding water for ball milling for 14-20 hours, drying, and crushing to obtain glass powder A and glass powder B for later use;
step 3, weighing the solvent, the ethyl cellulose, the resin, the flatting agent or the dispersing agent and the wetting agent according to the weight ratio, heating and stirring the mixture for 1 to 2 hours at the temperature of between 50 and 60 ℃, and uniformly mixing the mixture to obtain an organic carrier for later use;
and 4, weighing the silver powder, the glass powder, the inorganic additive, the carrier 1 and the carrier 2 according to the weight ratio, fully stirring and mixing, and further uniformly dispersing in a three-roll grinder, wherein the fineness of the obtained lead-free copper slurry is less than or equal to 6 microns.
10. The lead-free copper paste suitable for medium-temperature sintering of PZT sensors according to claim 9, wherein: in the step 2, the glass powder A is obtained by smelting for 30-60 min at the temperature of 1000-1200 ℃; the glass powder B is obtained by smelting for 60-90 min at 1200-1400 ℃.
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| CN101136261A (en) * | 2007-07-06 | 2008-03-05 | 广东风华高新科技股份有限公司 | Copper electrode slurry material and manufacturing method thereof |
| CN101339821A (en) * | 2008-08-15 | 2009-01-07 | 深圳市圣龙特电子有限公司 | Copper paste without lead and cadmium and manufacturing method therefor |
| CN111116239A (en) * | 2019-12-25 | 2020-05-08 | 西安英诺维特新材料有限公司 | Electronic paste suitable for PZT atomized sheet co-firing process and co-firing method |
| CN113724912A (en) * | 2021-08-27 | 2021-11-30 | 华昇电子材料(无锡)有限公司 | High-sintering compactness copper slurry for MLCC and preparation method thereof |
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2022
- 2022-02-18 CN CN202210152774.0A patent/CN114512260A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101136261A (en) * | 2007-07-06 | 2008-03-05 | 广东风华高新科技股份有限公司 | Copper electrode slurry material and manufacturing method thereof |
| CN101339821A (en) * | 2008-08-15 | 2009-01-07 | 深圳市圣龙特电子有限公司 | Copper paste without lead and cadmium and manufacturing method therefor |
| CN111116239A (en) * | 2019-12-25 | 2020-05-08 | 西安英诺维特新材料有限公司 | Electronic paste suitable for PZT atomized sheet co-firing process and co-firing method |
| CN113724912A (en) * | 2021-08-27 | 2021-11-30 | 华昇电子材料(无锡)有限公司 | High-sintering compactness copper slurry for MLCC and preparation method thereof |
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