CN102664056A - Conductive silver paste, preparation method of conductive silver paste, and surface metallization method for microwave dielectric ceramic - Google Patents
Conductive silver paste, preparation method of conductive silver paste, and surface metallization method for microwave dielectric ceramic Download PDFInfo
- Publication number
- CN102664056A CN102664056A CN2012101049548A CN201210104954A CN102664056A CN 102664056 A CN102664056 A CN 102664056A CN 2012101049548 A CN2012101049548 A CN 2012101049548A CN 201210104954 A CN201210104954 A CN 201210104954A CN 102664056 A CN102664056 A CN 102664056A
- Authority
- CN
- China
- Prior art keywords
- microwave
- conductive silver
- silver paste
- medium ceramics
- time
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a conductive silver paste and a preparation method of the conductive silver paste. The conductive silver paste comprises conductive silver powder, glass powder and an organic carrier; the conductive silver powder comprises micronsized conductive silver powder and nanosized conductive silver powder, wherein the conductive silver paste comprises the following components by mass: 52-72% of micronsized conductive silver powder, 10-20% of nanosized conductive silver powder, 3-9% of glass powder, and 15-25% of organic carrier. The invention also discloses a surface metallization method for a microwave dielectric ceramic, which comprises performing precise grinding, fine polishing, ultrasonic cleaning, first drying, screen printing with conductive silver paste, second drying and microwave sintering for the microwave medium ceramic. According to the conductive silver paste, the preparation method of the conductive silver paste, and the surface metallization method for the microwave dielectric ceramic, the preparation of the conductive silver paste is optimized, the microwave medium ceramic is precisely ground and finely polished before being printed with a silver film, and the silver film is sintered into a silver layer by the microwave sintering process, so that the surface adhesion of the metalized silver layer of the microwave medium ceramic can be increased, and the physical-chemical properties and the production efficiency of a metalized electrode of the microwave medium ceramic can be increased.
Description
Technical field
The present invention relates to the ceramic material field, particularly relate to the method for surface metallation of conductive silver paste and preparation method thereof, microwave-medium ceramics.
Background technology
Microwave-medium ceramics is meant the new function electron ceramic material that has the ceramic material of fabulous dielectric property in the microwave frequency range that is applied to 300MHz～300GHz and be applied in the microwave frequency band circuit to accomplish as dielectric material one or more functions, in microwave circuit, is bringing into play functions such as dielectric isolation, dielectric waveguide and dielectric resonance.
At present, the method for surface metallation of microwave-medium ceramics mainly contains silk screen printing sintering process, galvanoplastic, chemical etching sedimentation (comprise the nothing electricity, electro-deposition is arranged) and second metallization method etc.Normally used metallic electrode material has nickel, copper, silver, gold etc.Because the conductive capability of silver is strong, direct weld metal on silver-colored face, thermal coefficient of expansion is near porcelain base, Heat stability is good.And sintering temperature lower (700～900 ℃), sintering time is between 35～60min, and is not strict to the requirement of atmosphere, and sintering process is ripe, so silver is used comparatively extensive as the surface metalation electrode material.
Owing to consider environmental hazard and energy consumption, prior art adopts the silk screen printing sintering process more.But; Silver-colored slurry formula, silk screen printing parameter and the conventional silver slurry sintering process property of there are differences in the prior art; Often cause the silver layer of ceramic surface sintering smooth inadequately; And phenomenons such as peeling, foaming, pin hole and oxidation appear in silver layer ceramic surface after processing such as overaging, salt fog can cause sintering, can't satisfy the instructions for use of microwave electronic device.The kind of the kind of conductive silver paste and proportioning, particularly additive and consumption can influence parameters such as the surface adhesion force, sintering temperature, surface roughness of product, so industry is comparatively paid attention to for the prescription of conductive silver paste.Traditional conventional silver slurry sintering process sintering efficient is low, speed is slow, energy consumption is big, and the silver layer that sintering forms is oxidized easily.Oxidized in order to prevent that silver layer is exposed in the air, so take the ceramic product after multiple mode is deposited sintering, such as special-purpose storage box, special-purpose antifouling paper wood or vacuum bag etc., in use silver layer is oxidized but aforesaid way can't be avoided.
Summary of the invention
The technical problem that the present invention mainly solves provides the method for surface metallation of a kind of conductive silver paste and preparation method thereof, microwave-medium ceramics, forms the surface adhesion force that silver layer improves microwave-medium ceramics metallization silver layer through conductive silver paste, precise finiss and meticulous polishing and the microwave sintering process that uses special ratios.
For solving the problems of the technologies described above, the invention provides a kind of conductive silver paste, comprise conduction silver powder, glass dust and organic carrier, conduction silver powder comprises micron dimension conduction silver powder and nanometer scale conduction silver powder.Wherein, the mass percent of each component is in the conductive silver paste: micron dimension conduction silver powder 52～72%; Nanometer scale conduction silver powder 10～20%; Glass dust 3～9%; Organic carrier 15～25%.
Wherein, the mass percent of each component is in the conductive silver paste: micron dimension conduction silver powder 63%; Nanometer scale conduction silver powder 15%; Glass dust 5%; Organic carrier 17%.
Wherein, the particle size distribution of conductive silver paste is 0.2～2 μ m.
Wherein, micron dimension conduction silver powder is spherical, its mass fraction greater than 99.95%, particle size range is 0.8～2.0 μ m.
Wherein, nanometer scale conduction silver powder is spherical, its mass fraction greater than 99.95%, particle size range is 50～500nm.
Wherein, organic carrier comprises organic solvent, surfactant, antifoaming agent, anti-settling agent, thickener, coupling agent and plasticizer.
Wherein, Organic solvent is terpinol, ATBC or dibutyl phthalate, and surfactant is oleic acid, xylenes or lecithin, and antifoaming agent is polyethylene glycol, n-butanol or methyl-silicone oil; Anti-settling agent is a castor oil derivative; Thickener is an ethyl cellulose, and coupling agent is silane coupler or titanate coupling agent, and plasticizer is dibutyl phthalate, dioctyl phthalate or butyl carbitol acetate.
Wherein, The preparation method of above-mentioned conductive silver paste comprises: will analyze at least a in pure above bismuth oxide, boron oxide, silica and the zinc oxide and place vessel in heating to 1200～1500 ℃; Cool off after stirring, carry out ball milling after the quenching, obtain glass dust through the screening back; Carry out ball milling after glass dust, organic carrier and conduction silver powder mixed and make conductive silver paste.
Wherein, the preparation method of organic carrier is: organic solvent, surfactant, antifoaming agent, anti-settling agent, thickener, coupling agent and plasticizer are mixed to be placed on fully stir acquisition organic carrier in back in the thermostat water bath, wherein, bath temperature is 55～65 ℃.
For solving the problems of the technologies described above, the present invention also provides a kind of method for surface metallation of microwave-medium ceramics, and it adopts above-mentioned any described conductive silver paste, and this method may further comprise the steps: with the microwave-medium ceramics precise finiss; Under the effect of grinding agent with the meticulous polishing of the microwave-medium ceramics behind the precise finiss; With the microwave-medium ceramics ultrasonic cleaning after the meticulous polishing, to remove surface remaining grinding agent and spot; Microwave-medium ceramics after the ultrasonic cleaning is carried out the drying first time; Conductive silver paste placed on the silk screen dried microwave-medium ceramics is for the first time carried out silk screen printing, with surface printing silverskin at microwave-medium ceramics; Microwave-medium ceramics after the silk screen printing is carried out the drying second time; Dried microwave-medium ceramics carries out microwave sintering for the second time, forms silver layer on the surface of microwave-medium ceramics.
Wherein, the time of precise finiss is 8～10min.
Wherein, the time of ultrasonic cleaning is 5～15min.
Wherein, the size ratio of grinding agent is that 2: 1～8: 1, mass ratio are 2: 1～6: 1.
Wherein, the dry for the first time time is that 15～30min, temperature are 150～300 ℃.
Wherein, the dry for the second time time is that 15～30min, temperature are 100～150 ℃.
Wherein, the sintering time of microwave sintering is 3～8min, and peak temperature is 720～800 ℃, and microwave frequency is that 2.45GHz, power are 0.5～1.5KW.
The invention has the beneficial effects as follows: the situation that is different from prior art; The method for surface metallation of conductive silver paste of the present invention and preparation method thereof, microwave-medium ceramics is through the prescription of optimization conductive silver paste and before the printing silverskin, microwave-medium ceramics is carried out precise finiss and meticulous polishing; Through microwave sintering process silverskin is sintered to silver layer again; Can improve the surface adhesion force and the antioxygenic property of microwave-medium ceramics metallization silver layer, improve the physical and chemical performance and the production efficiency of microwave-medium ceramics metallic electrode.
Description of drawings
Fig. 1 is microscopic appearance ESEM (SEM) figure of the conductive silver paste of the embodiment of the invention one
Fig. 2 is the method for surface metallation flow chart of the microwave-medium ceramics of the embodiment of the invention three;
Fig. 3 is the temperature and time graph of a relation of microwave sintering and normal sintering in the method for surface metallation of microwave-medium ceramics of the present invention;
Fig. 4 is carrying out microwave sintering and carrying out silver layer ESEM (SEM) comparison diagram of normal sintering of the embodiment of the invention five.
Embodiment
To combine the accompanying drawing in the embodiment of the invention below, the technical scheme in the embodiment of the invention is carried out clear, intactly description, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
Embodiment one
See also Fig. 1, Fig. 1 is microscopic appearance ESEM (SEM) figure of the conductive silver paste of the embodiment of the invention one.
This conductive silver paste comprises conduction silver powder, glass dust and organic carrier, and conduction silver powder comprises micron dimension conduction silver powder and nanometer scale conduction silver powder.Among the figure, (A) be the microscopic appearance sem photograph of conductive silver paste, (B) for the microscopic appearance sem photograph of nanometer scale conduction silver powder, visible from figure, the granularity of conductive silver paste is between 0.2～2 μ m, and nanometer scale conduction silver powder is spherical.
Wherein, the mass percent of each component is in the conductive silver paste: micron dimension conductive silver 52～72%; Nanometer scale conduction silver powder 10～20%; Glass dust 3～9%; Organic carrier 15～25%, the particle size distribution of conductive silver paste are 0.2～2 μ m.In the present embodiment, the mass percent of each component is in the conductive silver paste: micron dimension conduction silver powder 63%; Nanometer scale conduction silver powder 15%; Glass dust 5%; Organic carrier 17%.
Conductive silver paste is a kind of electronic functional material that integrates metallurgy, chemical industry and electronic technology; Mainly by function phase, bonding phase and the phase composition that bonds temporarily; Be widely used in making thick film integrated circuit, resistor, resistor network, capacitor, chip multilayer ceramic capacitor (MLCC), electrode of solar battery, PDP electrode, printing and high-resolution electric conductor, thin film switch, conductive silver glue and other electronic devices and components.In the present embodiment, this conductive silver paste is used in microwave-medium ceramics surface sintering and forms silver layer as the surface metalation electrode material of microwave-medium ceramics.
Micron dimension conduction silver powder and nanometer scale conduction silver powder all are spherical; The mass fraction of micron dimension conduction silver powder greater than 99.95%, particle size range is 0.8～2.0 μ m, the mass fraction of nanometer scale conduction silver powder greater than 99.95%, particle size range is 50～500nm.Conduction silver powder plays heat conduction, electric action as the function phase of conductive silver paste.The conductive silver powder particles is dispersed in the conductive silver paste system with suspended state.
Glass dust is a kind of inorganic binder as the bonding phase of conductive silver paste, can bonding conduction silver powder and microwave-medium ceramics.Glass dust forms network-like tissue with conduction silver powder, regulates the thermal coefficient of expansion of conductive silver paste, to satisfy the requirement of adhesion strength.
Organic carrier comprises organic solvent, surfactant, antifoaming agent, anti-settling agent, thickener, coupling agent and plasticizer.Organic carrier is as the interim bonding phase of conductive silver paste, and bonding conduction silver powder and glass dust can make conductive silver paste and microwave-medium ceramics form preparatory the connection, and after the heating, organic carrier volatilizees immediately.The character of organic carrier, composition and content will influence thixotropy, levelability, compactness and the uniformity of conductive silver paste, and even have influence on the physical and chemical performance of microwave-medium ceramics surface metalation layer.
In the present embodiment; Organic solvent is terpinol, ATBC or dibutyl phthalate, and surfactant is oleic acid, xylenes or lecithin, and antifoaming agent is polyethylene glycol, n-butanol or methyl-silicone oil; Anti-settling agent is a castor oil derivative; Thickener is an ethyl cellulose, and coupling agent is silane coupler or titanate coupling agent, and plasticizer is dibutyl phthalate, dioctyl phthalate or butyl carbitol acetate.
Embodiment two
A kind of preparation method who implements the conductive silver paste of profit one, it comprises:
Step 1 is heated to 1200～1500 ℃ with at least a corundum crucible of analyzing in pure above bismuth oxide, boron oxide, silica and the zinc oxide that places, and cool off in cold water the back that stirs, and carries out ball milling after the quenching, and the back of sieving obtains glass dust.
Wherein, since not leaded in the raw material, so the glass dust that obtains is lead-free glass powder, compare the stronger flint glass powder of traditional toxicity, can not produce harm to environment.
Step 2 is placed on the abundant back acquisition organic carrier that stirs in the thermostat water bath with organic solvent, surfactant, antifoaming agent, anti-settling agent, thickener, coupling agent and plasticizer mixing, and wherein, bath temperature is 55～65 ℃.
Wherein, When conductive silver paste is coated on the microwave-medium ceramics surface; Conduct electricity between silver powder and the microwave-medium ceramics owing to receive the influence of many factors such as structure of density contrast, electric charge, cohesiveness, active force and dispersion; Occur conduction silver powder sedimentation phenomenon easily,, can solve this phenomenon and add anti-settling agent if the too fast meeting of sedimentation makes the conductive silver paste of ceramic surface produce sagging, phenomenon in uneven thickness.Antifoaming agent can be eliminated the bubble in the conductive silver paste.
Step 3 is carried out ball milling after glass dust, organic carrier and conduction silver powder mixed and is made conductive silver paste.
The conductive silver paste of this preparation method's preparation is applicable to microwave-medium ceramics; The surface printing silverskin of titanate base microwave dielectric ceramics particularly; The silverskin that is printed as and the surface combination property of microwave-medium ceramics are good, and surface adhesion force is strong, the silver layer surface smooth that forms behind the sintering.
Embodiment three
See also Fig. 2, Fig. 2 is the method for surface metallation flow chart of the microwave-medium ceramics of the embodiment of the invention three, adopts the conductive silver paste of embodiment one, and this method flow may further comprise the steps:
Step S101 is with the microwave-medium ceramics precise finiss.
Wherein, microwave-medium ceramics is fixed in precise finiss on the rotating disk of precision lapping machine with the vacuum suction mode, the time is 8～10min.Through precise finiss, can make microwave-medium ceramics attenuate 1～2mm.In other alternative alternative, can adopt fixedly microwave-medium ceramics of other fixed form.
Step S102, under the effect of grinding agent with the meticulous polishing of the microwave-medium ceramics behind the precise finiss.
Wherein, the microwave-medium ceramics behind the precise finiss is placed on the abrasive disk of meticulous polishing machine, under the grinding agent effect with the meticulous polishing of microwave-medium ceramics.The size ratio of grinding agent is that 2: 1～8: 1, mass ratio are 2: 1～6: 1.Through experimental verification; The line cutting mode that precise finiss that the present invention adopts and meticulous polished surface machining mode are compared prior art, its grinding efficiency improves 4～6 times, is not prone to phenomenons such as edges broken, breach; Effectively improve machining finished product rate; And the activity and the excellent adsorption on surface, processing back make conductive silver paste have better dispersiveness and uniformity on its surface, thereby improve the surface adhesion force of silver layer.
Step S103 is with the microwave-medium ceramics ultrasonic cleaning after the meticulous polishing, to remove surface remaining grinding agent and spot.
Wherein, place supersonic wave cleaning machine to carry out ultrasonic cleaning the microwave-medium ceramics after the meticulous polishing, the time is 5～15min.Ultrasonic cleaning is meant with ultrasonic wave and acts on cleaning solution; More effectively to remove the process of surface of the work greasy dirt and other impurity; Its principle is to utilize the cavitation of sonic oscillation to produce bubble; Bubble is squeezed and produces strong wallop when closed, dissolves the surface contaminant of cleaning object with this.
Step S104 carries out the drying first time with the microwave-medium ceramics after the ultrasonic cleaning.
Wherein, place far infrared stove to carry out the drying first time microwave-medium ceramics after the ultrasonic cleaning, the time is that 15～30min, temperature are 150～300 ℃.
Step S105 places conductive silver paste on the silk screen dried microwave-medium ceramics is for the first time carried out silk screen printing, with the surface printing silverskin at microwave-medium ceramics.
Wherein, Dried microwave-medium ceramics is put into anchor clamps and anchor clamps is placed screen process press for the first time; Conductive silver paste placed on the silk screen microwave-medium ceramics is carried out silk screen printing; Select mechanical parameters such as suitable scraper pressure and web plate order number according to predetermined silver film thickness, to obtain even, fine and close silver conductive film at the microwave-medium ceramics surface printing.In the present embodiment, can all print silverskin on two surfaces of microwave-medium ceramics.
Step S106 carries out the drying second time with the microwave-medium ceramics after the silk screen printing.
Wherein, place far infrared stove to carry out the drying second time microwave-medium ceramics after the silk screen printing, the time is that 15～30min, temperature are 100～150 ℃.
Step S107, dried microwave-medium ceramics carries out microwave sintering for the second time, forms silver layer on the surface of microwave-medium ceramics.
Wherein, For the second time dried microwave-medium ceramics is put into microwave silver ink firing stove (single mode or multimode) and is carried out microwave sintering, forms silver layer on the surface of microwave-medium ceramics, and sintering time is 3～8min; Peak temperature is 720～800 ℃, and microwave frequency is that 2.45GHz, power are 0.5～1.5KW.
Microwave is a kind of frequency electromagnetic waves, and its frequency range is 0.3～300GHz.Microwave sintering is to utilize that the dielectric loss of ceramic material makes ceramic material integral body be heated to sintering temperature and realize sintering and densification in the microwave electromagnetic field, and microwave frequency is mainly 2.45GHz.Under the microwave electromagnetic field action, ceramic material can produce a series of dielectric polarization, like electronic polarization, atom polarization, dipole pilot polarization and interfacial polarization etc., in microwave band, mainly is dipole polarization and interfacial polarization.The microcosmic particle kind of participating in polarization is different, and the time cycle of setting up or eliminating polarization is also different.Because the frequency of microwave electromagnetic field is very high; Make the inner dielectric polarization process of ceramic material can't follow the variation of external electric field; Polarization intensity vector P always lags behind electric field E; Cause producing the electric current with the electric field homophase, dissipate thereby constitute the inner medium of ceramic material, promptly the reciprocation of ceramic material and microwave causes ceramic material absorption microwave energy and is heated.The principle and the normal sintering of microwave sintering are essentially different: heat is by table diffusion inwards through ceramic material during normal sintering; Microwave sintering has then utilized the body heat characteristic of microwave; Be kinetic energy and the potential energy that microwave energy that ceramic material absorbs is converted into the material internal molecule, make the whole evenly heating simultaneously of ceramic material, so its heating and sintering velocity are very fast; And the inside and outside thermally equivalent simultaneously of material; Make ceramic material temperature inside gradient very little, thereby can make the material internal thermal stress reduce to minimum, this is highly beneficial for preparation high density, corrosion-resistant, high temperature resistant thick film metal electrode material.
Please consult Fig. 3 in the lump, Fig. 3 is the temperature and time graph of a relation of microwave sintering and normal sintering in the method for surface metallation of microwave-medium ceramics of the present invention.
Among the figure, abscissa express time, unit are min.Ordinate is represented temperature, and unit is ℃.The temperature and time graph of a relation of curve 21 expression microwave sinterings, the temperature and time graph of a relation of curve 22 expression normal sinterings.Comparison curves 21 can know that with curve 22 it is compared to normal sintering, and the microwave sintering time spent can shorten 7～10 times.
In addition, in the present embodiment, after the step S107, can also further comprise as required:
Microwave-medium ceramics after the electronickelling is carried out Performance Detection.
Wherein, adopt digital four point probe tester to record the surface resistivity≤2.0m Ω/S of silver layer, record surface adhesion force>=100N/ (2 * 2) mm of silver layer according to the GB/T17473.4-2008 national standard
2, and according to the welding performance of GB/T17473.7-1998 national standard test silver layer.This microwave-medium ceramics satisfies the instructions for use of microwave electronic device fully.
Embodiment four
A kind of method for surface metallation of microwave-medium ceramics, it comprises:
Step 1 for the column type microwave-medium ceramics resonator of 20mm is fixed in the vacuum suction mode on the rotating disk of precision lapping machine, through 8～10min precise finiss, makes its attenuate 2.0 ± 0.1mm with highly.
Step 2; The resonator that will pass through the step 1 processing places on the abrasive disk of meticulous polishing machine; Metal layer thickness according to predetermined is adjusted lap speed, under the grinding agent effect, resonator surface is carried out meticulous polishing 20min, makes its attenuate 0.1 ± 0.02mm; Wherein, the size ratio of grinding agent is that 6: 1, mass ratio are 4: 1.
Step 3, the resonator that will pass through the step 2 processing places supersonic wave cleaning machine to carry out ultrasonic cleaning 10min, to remove surface remaining lapping liquid and spot.
Step 4, the resonator that will pass through the step 3 processing places far infrared stove to carry out the drying first time, and wherein, the time is that 18min, temperature are 200 ℃.
Step 5; To pass through the resonator of step 4 processing and put into anchor clamps and place screen process press, conductive silver paste will be placed on the silk screen, and adopt 80 order web plates that resonator is carried out silk screen printing; Make conductive silver paste be uniformly coated on resonator surface, obtain even, fine and close silver conductive film.Wherein, the particle size distribution of conductive silver paste is 1.2 ± 0.1 μ m, and the mass percent of each component is in the conductive silver paste: micron dimension conduction silver powder 55%; Nanometer scale conduction silver powder 20%; Glass dust 7%; Organic carrier 18%.
Step 6, the resonator that will pass through the step 5 processing places far infrared stove to carry out the drying second time, and wherein, the time is 18min, and temperature is 110 ℃.
Step 7 will be passed through resonator that step 6 handles and sent in the microwave silver ink firing stove and carry out microwave sintering, form silver layer in resonator surface, and wherein, sintering time is 3min, and peak temperature is that 780 ℃, microwave frequency are that 2.45GHz, power are 1.5KW.
Step 8, the resonator that will pass through the step 7 processing adopts the surface resistivity of the digital four point probe tester test of SZ-82 silver layer.Surface adhesion force and welding performance according to GB/T17473.4-2008 and GB/T17473.7-1998 standard testing silver layer.The surface adhesion force that records silver layer is 145N/ (2 * 2) mm
2, surface resistivity is 1.42m Ω/S.
Present embodiment is applicable to titanate base microwave dielectric ceramics Related product.
Embodiment five
A kind of method for surface metallation of microwave-medium ceramics, it comprises:
Step 1 for the column type microwave-medium ceramics resonator of 20mm is fixed in the vacuum suction mode on the rotating disk of precision lapping machine, through 8～10min precise finiss, makes its attenuate 2.0 ± 0.1mm with highly.
Step 2, the resonator that will pass through the step 1 processing places on the abrasive disk of meticulous polishing machine, adjusts lap speed; Under the grinding agent effect, resonator surface is carried out meticulous polishing 20min; Make its attenuate 0.1 ± 0.02mm, wherein, the size ratio of grinding agent is that 6: 1, mass ratio are 4: 1.
Step 3, the resonator that will pass through the step 2 processing places supersonic wave cleaning machine to carry out ultrasonic cleaning 10min, to remove surface remaining lapping liquid and spot.
Step 4, the resonator that will pass through the step 3 processing places far infrared stove to carry out the drying first time, and wherein, the time is that 15min, temperature are 240 ℃.
Step 5; To pass through the resonator of step 4 processing and put into anchor clamps and place screen process press, conductive silver paste will be placed on the silk screen, and adopt 100 order web plates that resonator is carried out silk screen printing; Make conductive silver paste be uniformly coated on resonator surface, obtain even, fine and close silver conductive film.Wherein, the particle size distribution of conductive silver paste is 1.8 ± 0.1 μ m, and the mass percent of each component is in the conductive silver paste: micron dimension conduction silver powder 65%; Nanometer scale conduction silver powder 17%; Glass dust 5%; Organic carrier 13%.
Step 6, the resonator that will pass through the step 5 processing places far infrared stove to carry out the drying second time, and wherein, the time is 15min, and temperature is 125 ℃.
Step 7 will be passed through resonator that step 6 handles and sent in the microwave silver ink firing stove and carry out microwave sintering, form silver layer in resonator surface, and wherein, sintering time is 5min, and peak temperature is that 800 ℃, microwave frequency are that 2.45GHz, power are 1.0KW.
Step 8, the resonator that will pass through the step 7 processing adopts the surface resistivity of the digital four point probe tester test of SZ-82 silver layer.Surface adhesion force and welding performance according to GB/T17473.4-2008 and GB/T17473.7-1998 standard testing silver layer.The surface adhesion force that records silver layer is 169N/ (2 * 2) mm
2, surface resistivity is 1.16m Ω/S.
Present embodiment is applicable to titanate base microwave dielectric ceramics Related product.
Please consult Fig. 4 in the lump, Fig. 4 is carrying out microwave sintering and carrying out silver layer ESEM (SEM) comparison diagram of normal sintering of the embodiment of the invention five.
Among the figure,, (a) be this silver layer section S EM figure (A) for the resonator surface silverskin carries out the silver layer sem photograph that forms behind the normal sintering.(B), (b) be this silver layer section S EM figure for the resonator surface silverskin of embodiment five carries out the silver layer sem photograph that forms behind the microwave sintering.Behind contrast (A), (B) and the (a) and (b), can find out obviously that it is more even, fine and close to contain the silver layer that the conductive silver paste of nanometer scale conduction silver powder sinters into.
Embodiment six
A kind of method for surface metallation of microwave-medium ceramics, it comprises:
Step 1 for the column type microwave-medium ceramics resonator of 20mm is fixed in the vacuum suction mode on the rotating disk of precision lapping machine, through 8～10min precise finiss, makes its attenuate 2.0 ± 0.1mm with highly.
Step 2, the resonator that will pass through the step 1 processing places on the abrasive disk of meticulous polishing machine, adjusts lap speed; Under the grinding agent effect, resonator surface is carried out meticulous polishing 20min; Make its attenuate 0.1 ± 0.02mm, wherein, the size ratio of grinding agent is that 6: 1, mass ratio are 4: 1.
Step 3, the resonator that will pass through the step 2 processing places supersonic wave cleaning machine to carry out ultrasonic cleaning 10min, to remove surface remaining lapping liquid and spot.
Step 4, the resonator that will pass through the step 3 processing places far infrared stove to carry out the drying first time, and wherein, the time is that 20min, temperature are 150 ℃.
Step 5; To pass through the resonator of step 4 processing and put into anchor clamps and place screen process press, conductive silver paste will be placed on the silk screen, and adopt 120 order web plates that resonator is carried out silk screen printing; Make conductive silver paste be uniformly coated on resonator surface, obtain even, fine and close silver conductive film.Wherein, the particle size distribution of conductive silver paste is 1.5 ± 0.1 μ m, and the mass percent of each component is in the conductive silver paste: micron dimension conduction silver powder 70%; Nanometer scale conduction silver powder 10%; Glass dust 5%; Organic carrier 15%.
Step 6, the resonator that will pass through the step 5 processing places far infrared stove to carry out the drying second time, and wherein, the time is 15min, and temperature is 125 ℃.
Step 7 will be passed through resonator that step 6 handles and sent in the microwave silver ink firing stove and carry out microwave sintering, form silver layer in resonator surface, and wherein, sintering time is 7min, and peak temperature is that 750 ℃, microwave frequency are that 2.45GHz, power are 1.3KW.
Step 8, the resonator that will pass through the step 7 processing adopts the surface resistivity of the digital four point probe tester test of SZ-82 silver layer.Surface adhesion force and welding performance according to GB/T17473.4-2008 and GB/T17473.7-1998 standard testing silver layer.The surface adhesion force that records silver layer is 158N/ (2 * 2) mm
2, surface resistivity is 1.29m Ω/S.
Present embodiment is applicable to titanate base microwave dielectric ceramics Related product.
Embodiment seven
Adopt technological parameter with each component ratio different conductive silver paste identical with embodiment five; Microwave dielectric ceramic materials to making carries out performance test; Thereby the above embodiment of the present invention is applied to carries out labor in the concrete environment, the properties of sample index of gained is seen table 1.
Table 1 is the properties of sample index of raw material with the different conductive silver paste of each component ratio
Adopt the surface metalation electrode material of the conductive silver paste of the embodiment of the invention as microwave-medium ceramics; In conjunction with precise finiss and meticulous polished surface mechanical processing technique, silk screen printing and microwave sintering process; Surface adhesion force and the microwave-medium ceramics reliability of products and the solderability of silver layer and microwave-medium ceramics have been significantly improved; Overcome the shortcoming of phenomenons such as coming off appears in silver layer easily, pin hole, uneven thickness, and be not easy oxidized through the silver layer of microwave sintering.
By the way; The method for surface metallation of conductive silver paste of the present invention and preparation method thereof, microwave-medium ceramics is through the prescription of optimization conductive silver paste and before the printing silverskin, microwave-medium ceramics is carried out precise finiss and meticulous polishing; Through microwave sintering process silverskin is sintered to silver layer again; Can improve the surface adhesion force and the antioxygenic property of microwave-medium ceramics metallization silver layer, improve the physical and chemical performance and the production efficiency of microwave-medium ceramics metallic electrode.
The above is merely embodiments of the invention; Be not so limit claim of the present invention; Every equivalent structure or equivalent flow process conversion that utilizes specification of the present invention and accompanying drawing content to be done; Or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (16)
1. a conductive silver paste is characterized in that, comprises conduction silver powder, glass dust and organic carrier, and said conduction silver powder comprises micron dimension conduction silver powder and nanometer scale conduction silver powder, and wherein, the mass percent of each component is in the said conductive silver paste:
Micron dimension conduction silver powder 52～72%;
Nanometer scale conduction silver powder 10～20%;
Glass dust 3～9%;
Organic carrier 15～25%.
2. conductive silver paste according to claim 1 is characterized in that, the mass percent of each component is in the said conductive silver paste:
Micron dimension conduction silver powder 63%;
Nanometer scale conduction silver powder 15%;
Glass dust 5%;
Organic carrier 17%.
3. conductive silver paste according to claim 1 is characterized in that, the particle size distribution of said conductive silver paste is 0.2～2 μ m.
4. conductive silver paste according to claim 1 is characterized in that, said micron dimension conduction silver powder is spherical, its mass fraction greater than 99.95%, particle size range is 0.8～2.0 μ m.
5. conductive silver paste according to claim 1 is characterized in that, said nanometer scale conduction silver powder is spherical, its mass fraction greater than 99.95%, particle size range is 50～500nm.
6. conductive silver paste according to claim 1 is characterized in that said organic carrier comprises organic solvent, surfactant, antifoaming agent, anti-settling agent, thickener, coupling agent and plasticizer.
7. conductive silver paste according to claim 6; It is characterized in that; Said organic solvent is terpinol, ATBC or dibutyl phthalate, and said surfactant is oleic acid, xylenes or lecithin, and said antifoaming agent is polyethylene glycol, n-butanol or methyl-silicone oil; Said anti-settling agent is a castor oil derivative; Said thickener is an ethyl cellulose, and said coupling agent is silane coupler or titanate coupling agent, and said plasticizer is dibutyl phthalate, dioctyl phthalate or butyl carbitol acetate.
8. according to the preparation method of each described conductive silver paste of claim 1 to 7, it is characterized in that, comprising:
Place vessel in heating to 1200～1500 ℃ with analyzing at least a in pure above bismuth oxide, boron oxide, silica and the zinc oxide, cool off after stirring, carry out ball milling after the quenching, the back of sieving obtains glass dust;
Carry out ball milling after said conduction silver powder, glass dust and organic carrier mixed and make conductive silver paste.
9. method according to claim 8 is characterized in that, the preparation method of said organic carrier is:
Organic solvent, surfactant, antifoaming agent, anti-settling agent, thickener, coupling agent and plasticizer mixing are placed on the abundant back acquisition organic carrier that stirs in the thermostat water bath, and wherein, bath temperature is 55～65 ℃.
10. the method for surface metallation of a microwave-medium ceramics is characterized in that, adopts according to each described conductive silver paste of claim 1 to 7, said method comprising the steps of:
With said microwave-medium ceramics precise finiss;
Under the effect of grinding agent with the meticulous polishing of the microwave-medium ceramics behind the precise finiss;
With the microwave-medium ceramics ultrasonic cleaning after the meticulous polishing, to remove surface remaining grinding agent and spot;
Microwave-medium ceramics after the ultrasonic cleaning is carried out the drying first time;
Said conductive silver paste placed on the silk screen dried microwave-medium ceramics is for the first time carried out silk screen printing, with surface printing silverskin at said microwave-medium ceramics;
Microwave-medium ceramics after the silk screen printing is carried out the drying second time;
Dried microwave-medium ceramics carries out microwave sintering for the second time, forms silver layer on the surface of said microwave-medium ceramics.
11. method according to claim 10 is characterized in that, the time of said precise finiss is 8～10min.
12. method according to claim 10 is characterized in that, the time of said ultrasonic cleaning is 5～15min.
13. method according to claim 10 is characterized in that, the size ratio of said grinding agent is that 2: 1～8: 1, mass ratio are 2: 1～6: 1.
14. method according to claim 10 is characterized in that, the dry time of the said first time is that 15～30min, temperature are 150～300 ℃.
15. method according to claim 10 is characterized in that, the dry time of the said second time is that 15～30min, temperature are 100～150 ℃.
16. method according to claim 10 is characterized in that, the sintering time of said microwave sintering is 3～8min, and peak temperature is 720～800 ℃, and microwave frequency is that 2.45GHz, power are 0.5～1.5KW.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210104954.8A CN102664056B (en) | 2012-04-11 | 2012-04-11 | Conductive silver paste, preparation method of conductive silver paste, and surface metallization method for microwave dielectric ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210104954.8A CN102664056B (en) | 2012-04-11 | 2012-04-11 | Conductive silver paste, preparation method of conductive silver paste, and surface metallization method for microwave dielectric ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102664056A true CN102664056A (en) | 2012-09-12 |
| CN102664056B CN102664056B (en) | 2014-06-04 |
Family
ID=46773519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210104954.8A Active CN102664056B (en) | 2012-04-11 | 2012-04-11 | Conductive silver paste, preparation method of conductive silver paste, and surface metallization method for microwave dielectric ceramic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102664056B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103198880A (en) * | 2013-04-24 | 2013-07-10 | 海南大学 | Front-surface silver paste used for crystalline silicon solar cell and preparation method thereof |
| CN106952674A (en) * | 2017-02-24 | 2017-07-14 | 哈尔滨工业大学深圳研究生院 | It is a kind of can low-temperature sintering wiring thick film conductor paste and its application |
| CN111863312A (en) * | 2020-09-04 | 2020-10-30 | 西安宏星电子浆料科技股份有限公司 | Spraying type silver paste for 5G ceramic dielectric filter and preparation method thereof |
| CN113385678A (en) * | 2021-06-15 | 2021-09-14 | 深圳市宏博信息科技有限公司 | Preparation method of nano silver powder with high sintering activity |
| CN114155992A (en) * | 2021-11-29 | 2022-03-08 | 航天特种材料及工艺技术研究所 | High-adhesion conductive silver paste for ceramic matrix composite and preparation method thereof |
| CN115594517A (en) * | 2021-07-09 | 2023-01-13 | 惠州比亚迪电子有限公司（Cn） | Ceramic-metal composite part, preparation method thereof and electronic equipment |
| CN116890110A (en) * | 2023-09-11 | 2023-10-17 | 长春永固科技有限公司 | Micron silver powder capable of being sintered at low temperature and preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157574A (en) * | 2007-09-18 | 2008-04-09 | 湖南湘瓷科艺股份有限公司 | High-performance ceramic surface metallization process |
| CN101271928A (en) * | 2008-05-04 | 2008-09-24 | 常州亿晶光电科技有限公司 | High-viscosity solar cell front side silver paste and method for producing the same |
| CN101295739A (en) * | 2007-04-26 | 2008-10-29 | 比亚迪股份有限公司 | Conductive slurry for solar battery front side electrode and production method thereof |
| CN102368391A (en) * | 2011-10-26 | 2012-03-07 | 南昌大学 | High-conductivity lead-free silver paste used for crystalline silicon solar cell and preparation method thereof |
-
2012
- 2012-04-11 CN CN201210104954.8A patent/CN102664056B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101295739A (en) * | 2007-04-26 | 2008-10-29 | 比亚迪股份有限公司 | Conductive slurry for solar battery front side electrode and production method thereof |
| CN101157574A (en) * | 2007-09-18 | 2008-04-09 | 湖南湘瓷科艺股份有限公司 | High-performance ceramic surface metallization process |
| CN101271928A (en) * | 2008-05-04 | 2008-09-24 | 常州亿晶光电科技有限公司 | High-viscosity solar cell front side silver paste and method for producing the same |
| CN102368391A (en) * | 2011-10-26 | 2012-03-07 | 南昌大学 | High-conductivity lead-free silver paste used for crystalline silicon solar cell and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103198880A (en) * | 2013-04-24 | 2013-07-10 | 海南大学 | Front-surface silver paste used for crystalline silicon solar cell and preparation method thereof |
| CN106952674A (en) * | 2017-02-24 | 2017-07-14 | 哈尔滨工业大学深圳研究生院 | It is a kind of can low-temperature sintering wiring thick film conductor paste and its application |
| CN106952674B (en) * | 2017-02-24 | 2019-02-19 | 哈尔滨工业大学深圳研究生院 | It is a kind of can low-temperature sintering wiring thick film conductor paste and its application |
| CN111863312A (en) * | 2020-09-04 | 2020-10-30 | 西安宏星电子浆料科技股份有限公司 | Spraying type silver paste for 5G ceramic dielectric filter and preparation method thereof |
| CN113385678A (en) * | 2021-06-15 | 2021-09-14 | 深圳市宏博信息科技有限公司 | Preparation method of nano silver powder with high sintering activity |
| CN113385678B (en) * | 2021-06-15 | 2022-03-08 | 深圳市宏博信息科技有限公司 | Preparation method of nano silver powder with high sintering activity |
| CN115594517A (en) * | 2021-07-09 | 2023-01-13 | 惠州比亚迪电子有限公司（Cn） | Ceramic-metal composite part, preparation method thereof and electronic equipment |
| CN114155992A (en) * | 2021-11-29 | 2022-03-08 | 航天特种材料及工艺技术研究所 | High-adhesion conductive silver paste for ceramic matrix composite and preparation method thereof |
| CN116890110A (en) * | 2023-09-11 | 2023-10-17 | 长春永固科技有限公司 | Micron silver powder capable of being sintered at low temperature and preparation method |
| CN116890110B (en) * | 2023-09-11 | 2024-01-02 | 长春永固科技有限公司 | Micron silver powder capable of being sintered at low temperature and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102664056B (en) | 2014-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102664055B (en) | Conductive silver paste, method for preparing same and surface metallization method for microwave dielectric ceramics | |
| CN102664056B (en) | Conductive silver paste, preparation method of conductive silver paste, and surface metallization method for microwave dielectric ceramic | |
| CN104073660B (en) | A kind of flow casting molding prepares the method for soft magnetic metal composite | |
| CN100567189C (en) | Be used for dielectric glass powder, laminated ceramic capacitor and manufacture method thereof | |
| CN101321415B (en) | Rare earth thick film circuit electrical heating element based on aluminum nitride minicrystal ceramic substrates and its preparation technique | |
| CN105374412B (en) | Back of the body passivation back silver paste of solar cell and preparation method thereof, solar cell and preparation method thereof | |
| CN101483417B (en) | Preparation of black alumina substrate for multilayered wiring | |
| CN107316744B (en) | A kind of chip multilayer gold electrode chip capacitor and preparation method thereof | |
| CN102097183B (en) | Process for preparing conductive slurry for crystalline silicon solar cell front electrode | |
| CN104250442B (en) | Wave suction composite material and preparation method thereof, Meta Materials and application thereof | |
| CN101872653A (en) | Nano silver conductive paste and preparation method thereof | |
| CN106205935A (en) | A kind of amorphous state soft magnetism composite magnetic powder core and preparation method thereof | |
| KR20140098922A (en) | Electroconductive ink comoposition and method for forming an electrode by using the same | |
| CN104575663A (en) | Electrode slurry and preparation method thereof | |
| CN104361950A (en) | Preparation method of carbon-clad copper electronic paste | |
| CN101950597B (en) | Silver aluminum slurry for electromagnetic shielding and preparation method thereof | |
| CN100387905C (en) | Carbon crystal electrothermo-material and preparing method | |
| CN108962425A (en) | A kind of preparation method of graphene conductive slurry | |
| CN108352414A (en) | Sinterable composition for solar-energy photo-voltaic cell | |
| CN106653145A (en) | Medium-and-high temperature thick film circuit conductor paste and preparation method thereof | |
| CN109397786A (en) | A kind of heat loss through radiation can be around folding metallic aluminium base composite ceramic substrate and preparation method thereof | |
| CN108735343A (en) | A kind of conductive silver paste and preparation method thereof for low-temperature co-fired ceramic substrate | |
| CN105754512A (en) | Non-bright, anti-fingerprint and scraping-resistant single-side adhesive tape for conductive fabric and preparation method | |
| CN103031044B (en) | Protective paint for retarding or preventing migration of conductive silver ions, preparation method and application thereof | |
| CN108641250A (en) | A kind of multilevel hierarchy magnetic-dielectric composite wave-suction material and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180730 Address after: 233400 Huaiyuan County Economic Development Zone, Bengbu, Anhui Patentee after: Anhui Dafu Electromechanical Technology Co., Ltd. Address before: 518108 Floors 101, 2 and A4 of A1, A2, A3 in the Third Industrial Zone of Shajing Street, Shajing Street, Baoan District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Tat Fook Technology Co., Ltd. |