CN103274687B - Preparation method of low-temperature co-firing ceramic material with high dielectric constant - Google Patents
Preparation method of low-temperature co-firing ceramic material with high dielectric constant Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 19
- 238000010344 co-firing Methods 0.000 title abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000000843 powder Substances 0.000 claims abstract description 76
- 239000011521 glass Substances 0.000 claims abstract description 38
- 238000000227 grinding Methods 0.000 claims abstract description 31
- 238000000498 ball milling Methods 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 239000000919 ceramic Substances 0.000 claims abstract description 15
- 238000010791 quenching Methods 0.000 claims abstract description 8
- 230000000171 quenching effect Effects 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 26
- 238000009413 insulation Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- 229920005596 polymer binder Polymers 0.000 claims description 11
- 239000002491 polymer binding agent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000000748 compression moulding Methods 0.000 description 5
- 239000003989 dielectric material Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a preparation method of a low-temperature co-firing ceramic material with a high dielectric constant. The preparation method comprises the following steps of: A preparing raw ceramic powder; B stoving, pre-burning and crushing; C preparing glass powder; D stoving, fusing and crushing glass powder particles, namely discharging and filtering zirconia balls from a glass powder precursor raw material subjected to ball-milling in the step C, stoving at 100-120 DEG C, fusing and carrying out water quenching at 1450+/-50 DEG C, and finally crushing and grinding to the glass powder particles with the particle size of 200-300mu m; and E compounding, ball-milling, pelleting, tabletting and sintering the ceramic material. The preparation method is short in production cycle and low in cost and can be applied to transmission lines mainly containing microwave strip-shaped lines and passive electric circuit elements, such as a resonator, a coupler, a miniature filter, a capacitor and an electrical resistor utilizing the lines and the wave lengths of the transmission lines.
Description
Technical field
The present invention relates to a kind of preparation method of low temperature co-fired ceramic material with high dielectric constant
Background technology
Along with the fast development of microwave communication has expedited the emergence of third generation mobile (3G), in the world,, there is quite powerful short-wave communication tedhnology in country including Japan, Korea S, the U.S., Israel, the forefront in the Ye Zou world aspect the research of microwave dielectric material.And China's ability is in these areas quite weak, mainly comprise the three aspects :s such as microwave circuits, microwave dielectric material and device technology.Due to historical reasons, China's microwave device Multi-layer design thought sluggishness, Technology (being mainly precision) falls behind, and still there is no the microwave device of ability production high-performance, miniaturization.Therefore, although Multi-layer design thought is abroad put forward, we still cannot adopt the media ceramic of low-k to carry out the device design of miniaturization, and specific inductivity is unfavorable for improving too greatly again device use properties.From this two aspect, specific inductivity is slightly high, quality factor is high, easily practical microwave-medium ceramics is more practical way to select one.
In order to meet the efficient requirement utilizing of microwave resonator miniaturization and micro-wave energy, high performance microwave dielectric resonator should have the features such as volume is little, loss is low, frequency-temperature coefficient is little.Under microwave frequency, in the dielectric medium of resonance system, electromagnetic wavelength is inversely proportional to the square root (λ=λ of DIELECTRIC CONSTANT ε./εr
1/2，λ。For vacuum medium wavelength), under same resonant frequency, ε is larger, and in dielectric medium, microwave wavelength is just less, the size of corresponding dielectric resonator is just less, electromagnetic energy also more can concentrate in medium, is subject to surrounding environment influence also less, but in order to reduce the interference between transmission channel, ε again can not be too large (more than 100), thereby, require the specific inductivity of material to drop on suitable region, such as 58～70.In microwave region, loss is mainly to be produced by the interaction of external electromagnetic field and phonon, only possesses the microwave dielectric material of high quality factor, just likely makes resonator and the narrow bandwidth microwave resonator of low noise.The frequency-temperature coefficient τ of resonator
fmainly by coefficient of linear expansion α and temperature coefficient of permittivity τ
εcause, between them, meet: τ
f=-τ
ε/ 2-α.Dielectric resonator is all generally that resonant frequency using certain vibration modes of microwave dielectric material is as its mid-frequency, if τ
fexcessive, variation with temperature is produced large drift by the mid-frequency of device, thereby device cannot stably be worked, and α is generally 10ppm/ DEG C of left and right, thereby, require the τ of material
εlarger.Specific inductivity is high, loss is low, τ because have for pottery
fthe advantage such as less becomes the first-selection of microwave dielectric material.Microwave-medium ceramics has the features such as high dielectric constant, low-loss, near-zero frequency temperature coefficient except requiring.In addition, for the microwave-medium ceramics under specific works condition, also require physics, chemical stability high, material behavior rheological parameters' change with time rate is little, physical strength is large, thermal conductivity is large, and thermal diffusivity is good, and thermal expansivity is little, any surface finish, local defect is the least possible, good processing performance, with electrode without surface reaction etc.
The low sintering stupalith of can realizing using at present mainly comprises devitrified glass system, glass-ceramic compound system and amorphous glass system.Wherein devitrified glass system, glass+ceramics compound system are the emphasis of people's research in recent years.Many low fever ceramic systems is by extensive exploitation and utilization, as MgTiO
3-CaTiO
3system, (Zr, Sn) TiO
3-BaO-TiO
2system, BaO-Ln
2o
3-TiO
2system, Bi
2o
3-ZnO-Nb
2o
5system, BiNbO
4system, complex perovskite structure and tungsten bronze structured material system etc.
But preparation method's cost of existing stupalith is high, the production cycle is long, and easily to environment.
Therefore, be necessary to develop a kind of preparation method of new stupalith, to address the above problem.
Summary of the invention
The present invention proposes a kind of cost low, with short production cycle, there is the preparation method of a kind of low temperature co-fired ceramic material with high dielectric constant of low microwave-medium loss and less temperature coefficient of resonance frequency.It comprises the following steps:
A. the preparation steps of green powder, it comprises provides green powder precursor material, and green powder precursor material comprises the Li of 20～30 weight percents
2cO
3, the Nb of 45～55 weight percents
2o
5, the anatase titanium dioxide TiO of 20～30 weight percents
2, described green powder precursor material is added to solvent and zirconia ball, adopt wet ball grinding 10～12 hours;
B. oven dry, pre-burning, broken step, it comprises the zirconia ball in the green powder precursor material filtering out after steps A ball milling, and in 100～120 DEG C of oven dry, pre-burning at 900 ± 20 DEG C, it is the green powder of 200～300 μ m that last crushing grinding becomes particle diameter;
C. the preparation steps of glass powder, it comprises glass powder precursor material according to the ZnO of 15～25 weight percents; The H of 75～85 weight percents
3bO
3mix, add solvent and zirconia ball, adopt wet ball grinding 8～10 hours;
D. glass powder oven dry, melting, broken step, it comprises the glass powder precursor material discharging after C step ball milling is filtered out to zirconia ball, in 100～120 DEG C of oven dry, melt water quenching at 1450 ± 50 DEG C, it is the glass powder of 200～300 μ m that last crushing grinding becomes particle diameter;
E. composite, the ball milling of porcelain, granulation, compressing tablet, sintering step, it comprises that green powder that step B and step D are prepared and glass powder are according to the green powder of 97～99 weight percents; The glass powder of 1～3 weight percent mixes, and adds solvent and zirconia ball, adopts wet ball grinding 10～12 hours; Then add the high polymer binder aqueous solution of 5～15 weight percents, then ball milling 4～6 hours, mix granulation, compressing tablet, binder removal sintering.
On the basis of technique scheme, the specific inductivity of described low temperature co-fired ceramic material with high dielectric constant is 58～70@1MHz～3GHz, and dielectric loss is 0.001～0.003@1MHz～3GHz, resonance temperature factor τ
f=0 ± 15ppm/ DEG C, insulation resistivity ρ is 2.2 × 10
12Ω .cm～5.8 × 10
13Ω .cm.
On the basis of technique scheme, solvent described in described steps A, C, E is deionized water or dehydrated alcohol; Described zirconia ball is Φ 3mm～5mm.
On the basis of technique scheme, the weight proportion of the powder of green described in steps A precursor material, solvent, zirconia ball is 1: 0.8～1: 2.
On the basis of technique scheme, the weight proportion of glass powder precursor material, solvent, zirconia ball is 1: 0.8～1: 2 described in step C.
On the basis of technique scheme, the weight proportion of mixed powder, solvent, zirconia ball is 1: 0.8～1: 2 described in E step.
On the basis of technique scheme, the high polymer binder aqueous solution is polyvinyl butyral acetal or the polyvinyl alcohol water solution of 5～15 weight percents described in E step.
On the basis of technique scheme, binder removal sintering process described in step e comprises that ceramic plate is warmed up to 500 DEG C with the heat-up rate of 2 DEG C/min is incubated 1h, be warmed up to again 880 DEG C of insulation 10min, cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace.
Compared with prior art, advantage of the present invention is as follows: from preparation technology's angle, the cost of material is low easily buys, and is the common compound of chemical industry or oxide compound because raw materials used; Adopt conventional production unit processing, as ball mill, sintering oven, glass frit stove etc., without adding or research and develop large-scale professional equipment; The solid-phase synthesis that technique adopts is easier to control quality with respect to the technique such as sol-gel method, hydrothermal synthesis method; Sintering temperature is low, not only makes quality product easy to control, and meets energy-saving and emission-reduction requirement, therefore, preparation technology be generally stablize, economical, reliably, lay a good foundation for realizing rapidly industrialization.From meeting the need of market, this material dielectric constant is adjustable between 58～70@1MHz～3GHz, has low microwave-medium loss and less temperature coefficient of resonance frequency simultaneously, can meet the customized demand of user's seriation.From environment protection angle, the preparation method of this stupalith is energy-conservation, material-saving, green, environmental protection, meets RoHS Directive, not leaded Pb, cadmium Cd, mercury Hg, sexavalent chrome Cr
6+, the objectionable impurities such as Polybrominated biphenyl PBBs, Poly Brominated Diphenyl Ethers PBDEs, reduced to the full extent the environmental pollution bringing in raw material, waste material and production process.
Low-temperature co-fired microwave dielectric ceramic materials provided by the invention, can be applied to microstrip line and be main transmission route and utilize the passive electric circuit element such as resonator, coupling mechanism, wave filter miniaturization, electrical condenser, resistor of its circuit and wavelength.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described.
The preparation method of a kind of low temperature co-fired ceramic material with high dielectric constant of the present invention, it comprises the following steps:
The preparation steps of A green powder, it comprises provides green powder precursor material, and green powder precursor material comprises the Li of 20～30 weight percents
2cO
3, the Nb of 45～55 weight percents
2o
5, the anatase titanium dioxide TiO of 20～30 weight percents
2, described green powder precursor material is added to solvent and zirconia ball, adopt wet ball grinding 10～12 hours; The weight proportion of green powder precursor material, solvent, zirconia ball is 1: 0.8～1: 2.
B oven dry, pre-burning, broken step, it comprises the zirconia ball in the green powder precursor material filtering out after steps A ball milling, and in 100～120 DEG C of oven dry, pre-burning at 900 ± 20 DEG C, it is the green powder of 200～300 μ m that last crushing grinding becomes particle diameter;
The preparation steps of C glass powder, it comprises glass powder precursor material according to the ZnO of 15～25 weight percents; The H of 75～85 weight percents
3bO
3mix, add solvent and zirconia ball, adopt wet ball grinding 8～10 hours; The weight proportion of glass powder precursor material, solvent, zirconia ball is 1: 0.8～1: 2.
D. glass powder dry, dissolve, broken step, it comprises the glass powder precursor material discharging after C step ball milling is filtered out to zirconia ball, in 100～120 DEG C of oven dry, at 1450 ± 50 DEG C, dissolve shrend, it is the glass powder of 200～300 μ m that last crushing grinding becomes particle diameter;
E. composite, the ball milling of porcelain, granulation, compressing tablet, sintering step, it comprises that green powder that step B and step D are prepared and glass powder are according to the green powder of 97～99 weight percents; The glass powder of 1～3 weight percent mixes, and adds solvent and zirconia ball, adopts wet ball grinding 10～12 hours; Then add the high polymer binder aqueous solution of 5～15 weight percents, then ball milling 4～6 hours, mix granulation, compressing tablet, binder removal sintering.The weight proportion of mixed powder, solvent, zirconia ball is 1: 0.8～1: 2.The high polymer binder aqueous solution is polyvinyl butyral acetal or the polyvinyl alcohol water solution of 5～15 weight percents.Binder removal sintering process comprises that ceramic plate is warmed up to 500 DEG C with the heat-up rate of 2 DEG C/min is incubated 1h, then is warmed up to 880 DEG C of insulation 10min, cools to 400 DEG C with the cooling rate of 3 DEG C/min, cools to room temperature with the furnace.
The specific inductivity of low temperature co-fired ceramic material with high dielectric constant is 58～70@1MHz～3GHz, and dielectric loss is 0.001～0.003@1MHz～3GHz, resonance temperature factor τ
f=0 ± 15ppm/ DEG C, insulation resistivity ρ is 2.2 × 10
12Ω .cm～5.8 × 10
13Ω .cm.Solvent described in steps A, C, E is deionized water or dehydrated alcohol; Described zirconia ball is Φ 3mm～5mm.
Be described further below in conjunction with several groups of concrete embodiment.
Embodiment 1
Take 51.5g Li
2cO
3, 95.86g Nb
2o
5, 52.64g TiO
2mix, add 160g deionized water and 400g zirconia ball, adopt wet ball grinding 12 hours; Mixture after ball milling filters, and 120 DEG C of oven dry, then carries out pre-burning at 900 DEG C, grinds into the green powder particles of 200～300 μ m;
Take 80.25g H
3bO
3, 19.75g ZnO mixes, and adds 80g deionized water and 200g zirconia ball, adopts wet ball grinding 8 hours, the mixture after ball milling filters, and 120 DEG C of oven dry, then carries out melt water quenching at 1450 DEG C, grinds into the green powder particles of 200～300 μ m;
Take 98g green powder and 2g glass powder and mix, add 50g dehydrated alcohol and 200g zirconia ball, adopt wet ball grinding 12 hours; Add the PVB high polymer binder aqueous solution of 20ml, ball milling 5 hours, mixes, granulation compression molding; The ceramic plate pressing is warmed up to 500 DEG C of insulation 1h with the heat-up rate of 2 DEG C/min in kiln formula sintering oven, then is warmed up to 880 DEG C of insulation 10min; Cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace, take out print and carry out sanding and polishing, adopting agilent4991A to record specific inductivity is 60.5, dielectric loss is 0.0014, temperature coefficient of resonance frequency 9.5ppm/ DEG C, and insulation resistance is 4.3 × 10
12Ω .cm.
Embodiment 2
Take 42.3g Li
2cO
3, 108.72g Nb
2o
5, 48.98g TiO
2mix, add 160g deionized water and 400g zirconia ball, adopt wet ball grinding 10 hours; Mixture after ball milling filters, and 120 DEG C of oven dry, then carries out pre-burning at 900 DEG C, grinds into the green powder particles of 200～300 μ m;
Take 75g H
3bO
3, 25g ZnO mixes, and adds 80g deionized water and 200g zirconia ball, adopts wet ball grinding 10 hours, the mixture after ball milling filters, and 120 DEG C of oven dry, then carries out melt water quenching at 1450 DEG C, grinds into the green powder particles of 200～300 μ m;
Take 97g green powder and 3g glass powder and mix, add 50g dehydrated alcohol and 200g zirconia ball, adopt wet ball grinding 10 hours; Add the PVB high polymer binder aqueous solution of 22ml, ball milling 4 hours, mixes, granulation compression molding; The ceramic plate pressing is warmed up to 500 DEG C of insulation 1h with the heat-up rate of 2 DEG C/min in kiln formula sintering oven, then is warmed up to 880 DEG C of insulation 10min; Cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace, take out print and carry out sanding and polishing, adopting agilent4991A to record specific inductivity is 62.5, dielectric loss is 0.0016, temperature coefficient of resonance frequency 11.2ppm/ DEG C, and insulation resistance is 3.5 × 10
12Ω .cm.
Embodiment 3
Take 59g Li
2cO
3, 98.1g Nb
2o
5, 42.9g TiO
2mix, add 180g deionized water and 400g zirconia ball, adopt wet ball grinding 12 hours; Mixture after ball milling filters, and 120 DEG C of oven dry, then carries out pre-burning at 900 DEG C, grinds into the green powder particles of 200～300 μ m;
Take 84.5g H
3bO
3, 15.5g ZnO mixes, and adds 90g deionized water and 200g zirconia ball, adopts wet ball grinding 9 hours, the mixture after ball milling filters, and 120 DEG C of oven dry, then carries out melt water quenching at 1450 DEG C, grinds into the green powder particles of 200～300 μ m;
Take 99g green powder and 1g glass powder and mix, add 50g dehydrated alcohol and 200g zirconia ball, adopt wet ball grinding 11 hours; Add the PVB high polymer binder aqueous solution of 25ml, ball milling 6 hours, mixes, granulation compression molding; The ceramic plate pressing is warmed up to 500 DEG C of insulation 1h with the heat-up rate of 2 DEG C/min in kiln formula sintering oven, then is warmed up to 880 DEG C of insulation 10min; Cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace, take out print and carry out sanding and polishing, adopting agilent4991A to record specific inductivity is 59.4, dielectric loss is 0.0021, temperature coefficient of resonance frequency 8.2ppm/ DEG C, and insulation resistance is 3.2 × 10
12Ω .cm.
Embodiment 4
Take 46.5g Li
2cO
3, 94.6g Nb
2o
5, 58.9g TiO
2mix, add 160g deionized water and 400g zirconia ball, adopt wet ball grinding 12 hours; Mixture after ball milling filters, and 120 DEG C of oven dry, then carries out pre-burning at 900 DEG C, grinds into the green powder particles of 200～300 μ m;
Take 80.25g H
3bO
3, 19.75g ZnO mixes, and adds 80g deionized water and 200g zirconia ball, adopts wet ball grinding 10 hours, the mixture after ball milling filters, and 120 DEG C of oven dry, then carries out melt water quenching at 1450 DEG C, grinds into the green powder particles of 200～300 μ m;
Take 98g green powder and 2g glass powder and mix, add 50g dehydrated alcohol and 200g zirconia ball, adopt wet ball grinding 10 hours; Add the PVB high polymer binder aqueous solution of 20ml, ball milling 4 hours, mixes, granulation compression molding; The ceramic plate pressing is warmed up to 500 DEG C of insulation 1h with the heat-up rate of 2 DEG C/min in kiln formula sintering oven, then is warmed up to 880 DEG C of insulation 10min; Cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace, take out print and carry out sanding and polishing, adopting agilent4991A to record specific inductivity is 67.2, dielectric loss is 0.0017, temperature coefficient of resonance frequency 8.8ppm/ DEG C, and insulation resistance is 2.9 × 10
12Ω .cm.
Embodiment 5
Take 55.1g Li
2cO
3, 97.28g Nb
2o
5, 47.62g TiO
2mix, add 160g deionized water and 400g zirconia ball, adopt wet ball grinding 10 hours; Mixture after ball milling filters, and 120 DEG C of oven dry, then carries out pre-burning at 900 DEG C, grinds into the green powder particles of 200～300 μ m;
Take 64.53gH
3bO
3, 35.47g ZnO mixes, and adds 80g deionized water and 200g zirconia ball, adopts wet ball grinding 12 hours, the mixture after ball milling filters, and 120 DEG C of oven dry, then carries out melt water quenching at 1450 DEG C, grinds into the green powder particles of 200～300 μ m;
Take 97g green powder and 3g glass powder and mix, add 50g dehydrated alcohol and 200g zirconia ball, adopt wet ball grinding 10 hours; Add the PVB high polymer binder aqueous solution of 22ml, ball milling 4 hours, mixes, granulation compression molding; The ceramic plate pressing is warmed up to 500 DEG C of insulation 1h with the heat-up rate of 2 DEG C/min in kiln formula sintering oven, then is warmed up to 880 DEG C of insulation 10min; Cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace, take out print and carry out sanding and polishing, adopting agilent4991A to record specific inductivity is 64.8, dielectric loss is 0.0025, temperature coefficient of resonance frequency 13ppm/ DEG C, and insulation resistance is 5.4 × 10
12Ω .cm.
Table 1 embodiment of the present invention products obtained therefrom performance comparison
As known from Table 1, all samples all can be at the lower sintering of middle low temperature (Ts≤900 DEG C); Specific inductivity 58～70@1MHz～3GHz of sample, dielectric loss is 0.001～0.003@1MHz～3GHz, resonance temperature factor τ
f=0 ± 15ppm/ DEG C, insulation resistivity ρ is 2.2 × 10
12Ω .cm～5.8 × 10
13Ω .cm.
Claims (8)
1. a preparation method for low temperature co-fired ceramic material with high dielectric constant, is characterized in that: it comprises the following steps:
A. the preparation steps of green powder, it comprises provides green powder precursor material, and green powder precursor material comprises the Li of 20～30 weight percents
2cO
3, the Nb of 45～55 weight percents
2o
5, the anatase titanium dioxide TiO of 20～30 weight percents
2, described green powder precursor material is added to solvent and zirconia ball, adopt wet ball grinding 10～12 hours;
B. oven dry, pre-burning, broken step, it comprises the zirconia ball in the green powder precursor material filtering out after steps A ball milling, and in 100～120 DEG C of oven dry, pre-burning at 900 ± 20 DEG C, it is the green powder of 200～300 μ m that last crushing grinding becomes particle diameter;
C. the preparation steps of glass powder, it comprises glass powder precursor material according to the ZnO of 15～25 weight percents; The H of 75～85 weight percents
3bO
3mix, add solvent and zirconia ball, adopt wet ball grinding 8～10 hours;
D. glass powder oven dry, melting, broken step, it comprises the glass powder precursor material discharging after C step ball milling is filtered out to zirconia ball, in 100～120 DEG C of oven dry, melt water quenching at 1450 ± 50 DEG C, it is the glass powder of 200～300 μ m that last crushing grinding becomes particle diameter;
E. composite, the ball milling of porcelain, granulation, compressing tablet, sintering step, it comprises that green powder that step B and step D are prepared and glass powder are according to the green powder of 97～99 weight percents; The glass powder of 1～3 weight percent mixes, and adds solvent and zirconia ball, adopts wet ball grinding 10～12 hours; Then add the high polymer binder aqueous solution of 5～15 weight percents, then ball milling 4～6 hours, mix granulation, compressing tablet, binder removal sintering.
2. the preparation method of a kind of low temperature co-fired ceramic material with high dielectric constant as claimed in claim 1, it is characterized in that: the specific inductivity of described low temperature co-fired ceramic material with high dielectric constant is 58～70@1MHz～3GHz, dielectric loss is 0.001～0.003@1MHz～3GHz, resonance temperature factor τ f=0 ± 15ppm/ DEG C, insulation resistivity ρ is 2.2 × 10
12Ω .cm～5.8 × 10
13Ω .cm.
3. the preparation method of a kind of low temperature co-fired ceramic material with high dielectric constant as claimed in claim 1, is characterized in that: solvent described in described steps A, C, E is deionized water or dehydrated alcohol; Described zirconia ball is Φ 3mm～5mm.
4. the preparation method of a kind of low temperature co-fired ceramic material with high dielectric constant as claimed in claim 1, is characterized in that: the weight proportion of the powder of green described in steps A precursor material, solvent, zirconia ball is 1: 0.8～1: 2.
5. the preparation method of a kind of low temperature co-fired ceramic material with high dielectric constant as claimed in claim 1, is characterized in that: described in C step, the weight proportion of glass powder precursor material, solvent, zirconia ball is 1: 0.8～1: 2.
6. the preparation method of a kind of low temperature co-fired ceramic material with high dielectric constant as claimed in claim 1, is characterized in that: described in E step, the weight proportion of mixed powder, solvent, zirconia ball is 1: 0.8～1: 2.
7. the preparation method of a kind of low temperature co-fired ceramic material with high dielectric constant as claimed in claim 1, is characterized in that: described in E step, the high polymer binder aqueous solution is polyvinyl butyral acetal or the polyvinyl alcohol water solution of 5～15 weight percents.
8. the preparation method of a kind of low temperature co-fired ceramic material with high dielectric constant as claimed in claim 1, it is characterized in that: the binder removal sintering process described in step e comprises that ceramic plate is warmed up to 500 DEG C with the heat-up rate of 2 DEG C/min is incubated 1h, be warmed up to again 880 DEG C of insulation 10min, cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace.
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| US6316376B1 (en) * | 2000-11-17 | 2001-11-13 | Kug Sun Hong | Dielectric ceramic compositions and method of preparation therefor |
| CN1915904A (en) * | 2006-08-29 | 2007-02-21 | 中国科学院上海硅酸盐研究所 | Low temperature sintered composite microwave medium ceramic in series of lithium, niobium and titanium, and prepartion method |
| CN1974479A (en) * | 2006-12-07 | 2007-06-06 | 华南理工大学 | Low temperature sintered high frequency heat stable dielectric ceramic and its prepn process |
| CN101215159A (en) * | 2007-12-28 | 2008-07-09 | 天津大学 | Low-temperature sintering low-loss high frequency medium ceramic and preparing method thereof |
| CN101613200A (en) * | 2009-07-21 | 2009-12-30 | 西安交通大学 | A kind of low-temperature sintered microwave dielectric ceramic material and preparation method thereof |
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| US6316376B1 (en) * | 2000-11-17 | 2001-11-13 | Kug Sun Hong | Dielectric ceramic compositions and method of preparation therefor |
| CN1915904A (en) * | 2006-08-29 | 2007-02-21 | 中国科学院上海硅酸盐研究所 | Low temperature sintered composite microwave medium ceramic in series of lithium, niobium and titanium, and prepartion method |
| CN1974479A (en) * | 2006-12-07 | 2007-06-06 | 华南理工大学 | Low temperature sintered high frequency heat stable dielectric ceramic and its prepn process |
| CN101215159A (en) * | 2007-12-28 | 2008-07-09 | 天津大学 | Low-temperature sintering low-loss high frequency medium ceramic and preparing method thereof |
| CN101613200A (en) * | 2009-07-21 | 2009-12-30 | 西安交通大学 | A kind of low-temperature sintered microwave dielectric ceramic material and preparation method thereof |
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Denomination of invention: A Preparation Method for High Dielectric Constant Low Temperature Co fired Ceramic Materials Effective date of registration: 20230421 Granted publication date: 20141203 Pledgee: Huaxia Bank Limited by Share Ltd. Kunming Chenggong Pledgor: YUNNAN INFINE NEO-MATERIAL Co.,Ltd. Registration number: Y2023530000024 |
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