CN103274687A - 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
- 239000000463 material Substances 0.000 claims description 30
- 238000009413 insulation Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 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
- 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
- 238000000034 method Methods 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
- 239000002131 composite material Substances 0.000 claims description 4
- 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
- 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
- 230000004927 fusion 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
- 238000001914 filtration Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 15
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 5
- 239000003989 dielectric material Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004891 communication 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
- 230000008901 benefit Effects 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
- 238000006243 chemical reaction Methods 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 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
- 238000012545 processing Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis 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 high-k low-temperature co-burning ceramic material
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 the country that comprises Japan, Korea S, the U.S., Israel, in the forefront of also walking aspect the research of microwave dielectric material in the world.And China's ability in these areas is quite weak, mainly comprises three aspects such as microwave circuits, microwave dielectric material and device technology.Since historical reasons, China's microwave device multilayer design philosophy sluggishness, and Technology (mainly being precision) falls behind, and does not still have the microwave device of ability production high-performance, miniaturization.Therefore, although the multilayer design philosophy is abroad put forward, the designs that we still can't adopt the media ceramic of low-k to carry out miniaturization, specific inductivity is unfavorable for improving the device use properties too greatly again.From this two aspect, specific inductivity is high slightly, quality factor is high, the microwave-medium ceramics of easy practicability is more practical way to select one.
In order to satisfy the efficient requirement that utilizes of microwave resonator miniaturization and micro-wave energy, high performance microwave dielectric resonator should have characteristics 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./εr
1/2，λ。Be the vacuum medium wavelength), under same resonant frequency, ε is more big, and microwave wavelength is just more little in the dielectric medium, the size of corresponding dielectric resonator is just more little, electromagnetic energy also more can concentrate in the medium, is subjected to surrounding environment influence also more little, yet in order to reduce the interference between transmission channel, ε again can not be too big (more than 100), thereby, require the specific inductivity of material to drop on suitable zone, such as 58～70.In microwave region, loss mainly is to be produced by the interaction of external electromagnetic field and phonon, only possesses the microwave dielectric material of high quality factor, just might make resonator and the narrow bandwidth microwave resonator of low noise.The frequency-temperature coefficient τ of resonator
fMainly be by coefficient of linear expansion α and temperature coefficient of permittivity τ
εCause, satisfy between them: τ
f=-τ
ε/ 2-α.Dielectric resonator generally all is that resonant frequency with certain vibration modes of microwave dielectric material is as its mid-frequency, if τ
fExcessive, then the mid-frequency of device will produce big drift with variation of temperature, thereby device can't stably be worked, and α is generally about 10ppm/ ℃, thereby, require the τ of material
εBigger.Pottery is because have specific inductivity height, low, the τ of loss
fAdvantage such as less becomes the first-selection of microwave dielectric material.Microwave-medium ceramics has characteristics such as high dielectric constant, low-loss, near-zero frequency temperature coefficient except requiring.In addition, for the microwave-medium ceramics under the concrete working conditions, also require physics, chemical stability height, material behavior through the time velocity of variation little, physical strength is big, thermal conductivity is big, and thermal diffusivity is good, and thermal expansivity is little, any surface finish, local defect is the least possible, and the favorable manufacturability energy does not have interface reaction etc. with electrode.
The low sintering stupalith of can realizing that uses mainly comprises devitrified glass system, glass-ceramic compound system and amorphous glass system at present.Wherein devitrified glass system, glass+Ceramic Composite 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 height of existing stupalith, the production cycle is long, and easily environment is polluted.
Therefore, be necessary to develop a kind of preparation method of new stupalith, to address the above problem.
Summary of the invention
It is low to the present invention proposes a kind of cost, with short production cycle, has the preparation method of a kind of high-k low-temperature co-burning ceramic material of low microwave-medium loss and less temperature coefficient of resonance frequency.It may further comprise the 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 solvent and zirconia ball, adopted wet ball grinding 10～12 hours;
B. oven dry, pre-burning, broken step, it comprises the zirconia ball in the green powder precursor material that filters out behind the steps A ball milling, and in 100～120 ℃ of oven dry, 900 ± 20 ℃ of following pre-burnings, 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 the ZnO of glass powder precursor material according to 15～25 weight percents; The H of 75～85 weight percents
3BO
3Mix, add solvent and zirconia ball, adopted wet ball grinding 8～10 hours;
D. glass powder oven dry, fusion, broken step, it comprises the glass powder precursor material discharging behind C step ball milling is filtered out zirconia ball, in 100～120 ℃ of oven dry, at 1450 ± 50 ℃ of following melt water quenchings, 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; The high polymer binder aqueous solution that adds 5～15 weight percents then, ball milling is 4～6 hours again, mixes granulation, compressing tablet, binder removal sintering.
On the basis of technique scheme, the specific inductivity of described high-k low-temperature co-burning ceramic material is 58～70@1MHz～3GHz, and dielectric loss is 0.001～0.003@1MHz～3GHz, resonance temperature factor τ
f=0 ± 15ppm/ ℃, 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, the 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 the described glass powder precursor material of step C, solvent, zirconia ball is 1: 0.8～1: 2.
On the basis of technique scheme, the weight proportion of the described mixed powder of E step, solvent, zirconia ball is 1: 0.8～1: 2.
On the basis of technique scheme, polyvinyl butyral acetal or polyvinyl alcohol water solution that the described high polymer binder aqueous solution of E step is 5～15 weight percents.
On the basis of technique scheme, the described binder removal sintering process of step e comprises ceramic plate is warmed up to 500 ℃ of insulation 1h with the heat-up rate of 2 ℃/min, be warmed up to 880 ℃ of insulation 10min again, cool to 400 ℃ with the cooling rate of 3 ℃/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, because the raw materials used common compound of chemical industry or the oxide compound of being; Adopt conventional production unit processing, as ball mill, sintering oven, glass frit stove etc., need not to acquire or research and develop large-scale professional equipment; The solid-phase synthesis that technology adopts is easier to control quality with respect to technologies such as sol-gel method, hydrothermal synthesis methods; Sintering temperature is low, not only makes quality product easy to control, and satisfies the energy-saving and emission-reduction requirement, therefore, preparation technology be generally stablize, economical, reliably, lay a good foundation for realizing industrialization rapidly.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 satisfy the customized demand of user's seriation.From the environment protection angle, the preparation method of this stupalith is energy-conservation, material-saving, green, environmental protection, meets the RoHS of European Union instruction, not leaded Pb, cadmium Cd, mercury Hg, sexavalent chrome Cr
6+, objectionable impuritiess such as Polybrominated biphenyl PBBs, Poly Brominated Diphenyl Ethers PBDEs, reduced the environmental pollution that brings in raw material, waste material and the production process to the full extent.
Low-temperature co-fired microwave dielectric ceramic materials provided by the invention, the passive electric circuit elements such as resonator, coupling mechanism, wave filter miniaturization, electrical condenser, resistor that can be applied to microstrip line and be main transmission route and utilize its circuit and wavelength.
Embodiment
Below in conjunction with specific embodiment, the present invention is further specified.
The preparation method of a kind of high-k low-temperature co-burning ceramic material of the present invention, it may further comprise the 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 solvent and zirconia ball, adopted 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 that filters out behind the steps A ball milling, and in 100～120 ℃ of oven dry, 900 ± 20 ℃ of following pre-burnings, 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 the ZnO of glass powder precursor material according to 15～25 weight percents; The H of 75～85 weight percents
3BO
3Mix, add solvent and zirconia ball, adopted wet ball grinding 8～10 hours; The weight proportion of glass powder precursor material, solvent, zirconia ball is 1: 0.8～1: 2.
D. the glass powder dry, dissolve, broken step, it comprises the glass powder precursor material discharging behind C step ball milling is filtered out zirconia ball, in 100～120 ℃ of oven dry, under 1450 ± 50 ℃, 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; The high polymer binder aqueous solution that adds 5～15 weight percents then, ball milling is 4～6 hours again, mixes 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.The binder removal sintering process comprises ceramic plate is warmed up to 500 ℃ of insulation 1h with the heat-up rate of 2 ℃/min, is warmed up to 880 ℃ of insulation 10min again, cools to 400 ℃ with the cooling rate of 3 ℃/min, cools to room temperature with the furnace.
The specific inductivity of high-k low-temperature co-burning ceramic material is 58～70@1MHz～3GHz, and dielectric loss is 0.001～0.003@1MHz～3GHz, resonance temperature factor τ
f=0 ± 15ppm/ ℃, insulation resistivity ρ is 2.2 * 10
12Ω .cm～5.8 * 10
13Ω .cm.Solvent described in steps A, C, the 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 by weighing 51.5g Li
2CO
3, 95.86g Nb
2O
5, 52.64g TiO
2Mix, add 160g deionized water and 400g zirconia ball, adopted wet ball grinding 12 hours; Mixture behind ball milling filters, and 120 ℃ of oven dry, carries out pre-burning at 900 ℃ again, grinds into the green powder particles of 200～300 μ m;
Take by weighing 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 behind ball milling filters, and 120 ℃ of oven dry, carries out melt water quenching at 1450 ℃ again, grinds into the green powder particles of 200～300 μ m;
Take by weighing 98g green powder and 2g glass powder and mix, add 50g dehydrated alcohol and 200g zirconia ball, adopted wet ball grinding 12 hours; The PVB high polymer binder aqueous solution that adds 20ml, ball milling 5 hours mixes, the granulation compression molding; The ceramic plate heat-up rate with 2 ℃/min in kiln formula sintering oven that presses is warmed up to 500 ℃ of insulation 1h, is warmed up to 880 ℃ of insulation 10min again; Cooling rate with 3 ℃/min cools to 400 ℃, cools to room temperature with the furnace, takes out print and carries out sanding and polishing, adopting agilent4991A to record specific inductivity is 60.5, dielectric loss is 0.0014, and temperature coefficient of resonance frequency 9.5ppm/ ℃, insulation resistance is 4.3 * 10
12Ω .cm.
Embodiment 2
Take by weighing 42.3g Li
2CO
3, 108.72g Nb
2O
5, 48.98g TiO
2Mix, add 160g deionized water and 400g zirconia ball, adopted wet ball grinding 10 hours; Mixture behind ball milling filters, and 120 ℃ of oven dry, carries out pre-burning at 900 ℃ again, grinds into the green powder particles of 200～300 μ m;
Take by weighing 75g H
3BO
3, 25g ZnO mixes, and adds 80g deionized water and 200g zirconia ball, adopts wet ball grinding 10 hours, the mixture behind ball milling filters, and 120 ℃ of oven dry, carries out melt water quenching at 1450 ℃ again, grinds into the green powder particles of 200～300 μ m;
Take by weighing 97g green powder and 3g glass powder and mix, add 50g dehydrated alcohol and 200g zirconia ball, adopted wet ball grinding 10 hours; The PVB high polymer binder aqueous solution that adds 22ml, ball milling 4 hours mixes, the granulation compression molding; The ceramic plate heat-up rate with 2 ℃/min in kiln formula sintering oven that presses is warmed up to 500 ℃ of insulation 1h, is warmed up to 880 ℃ of insulation 10min again; Cooling rate with 3 ℃/min cools to 400 ℃, cools to room temperature with the furnace, takes out print and carries out sanding and polishing, adopting agilent4991A to record specific inductivity is 62.5, dielectric loss is 0.0016, and temperature coefficient of resonance frequency 11.2ppm/ ℃, insulation resistance is 3.5 * 10
12Ω .cm.
Embodiment 3
Take by weighing 59g Li
2CO
3, 98.1g Nb
2O
5, 42.9g TiO
2Mix, add 180g deionized water and 400g zirconia ball, adopted wet ball grinding 12 hours; Mixture behind ball milling filters, and 120 ℃ of oven dry, carries out pre-burning at 900 ℃ again, grinds into the green powder particles of 200～300 μ m;
Take by weighing 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 behind ball milling filters, and 120 ℃ of oven dry, carries out melt water quenching at 1450 ℃ again, grinds into the green powder particles of 200～300 μ m;
Take by weighing 99g green powder and 1g glass powder and mix, add 50g dehydrated alcohol and 200g zirconia ball, adopted wet ball grinding 11 hours; The PVB high polymer binder aqueous solution that adds 25ml, ball milling 6 hours mixes, the granulation compression molding; The ceramic plate heat-up rate with 2 ℃/min in kiln formula sintering oven that presses is warmed up to 500 ℃ of insulation 1h, is warmed up to 880 ℃ of insulation 10min again; Cooling rate with 3 ℃/min cools to 400 ℃, cools to room temperature with the furnace, takes out print and carries out sanding and polishing, adopting agilent4991A to record specific inductivity is 59.4, dielectric loss is 0.0021, and temperature coefficient of resonance frequency 8.2ppm/ ℃, insulation resistance is 3.2 * 10
12Ω .cm.
Embodiment 4
Take by weighing 46.5g Li
2CO
3, 94.6g Nb
2O
5, 58.9g TiO
2Mix, add 160g deionized water and 400g zirconia ball, adopted wet ball grinding 12 hours; Mixture behind ball milling filters, and 120 ℃ of oven dry, carries out pre-burning at 900 ℃ again, grinds into the green powder particles of 200～300 μ m;
Take by weighing 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 behind ball milling filters, and 120 ℃ of oven dry, carries out melt water quenching at 1450 ℃ again, grinds into the green powder particles of 200～300 μ m;
Take by weighing 98g green powder and 2g glass powder and mix, add 50g dehydrated alcohol and 200g zirconia ball, adopted wet ball grinding 10 hours; The PVB high polymer binder aqueous solution that adds 20ml, ball milling 4 hours mixes, the granulation compression molding; The ceramic plate heat-up rate with 2 ℃/min in kiln formula sintering oven that presses is warmed up to 500 ℃ of insulation 1h, is warmed up to 880 ℃ of insulation 10min again; Cooling rate with 3 ℃/min cools to 400 ℃, cools to room temperature with the furnace, takes out print and carries out sanding and polishing, adopting agilent4991A to record specific inductivity is 67.2, dielectric loss is 0.0017, and temperature coefficient of resonance frequency 8.8ppm/ ℃, insulation resistance is 2.9 * 10
12Ω .cm.
Embodiment 5
Take by weighing 55.1g Li
2CO
3, 97.28g Nb
2O
5, 47.62g TiO
2Mix, add 160g deionized water and 400g zirconia ball, adopted wet ball grinding 10 hours; Mixture behind ball milling filters, and 120 ℃ of oven dry, carries out pre-burning at 900 ℃ again, grinds into the green powder particles of 200～300 μ m;
Take by weighing 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 behind ball milling filters, and 120 ℃ of oven dry, carries out melt water quenching at 1450 ℃ again, grinds into the green powder particles of 200～300 μ m;
Take by weighing 97g green powder and 3g glass powder and mix, add 50g dehydrated alcohol and 200g zirconia ball, adopted wet ball grinding 10 hours; The PVB high polymer binder aqueous solution that adds 22ml, ball milling 4 hours mixes, the granulation compression molding; The ceramic plate heat-up rate with 2 ℃/min in kiln formula sintering oven that presses is warmed up to 500 ℃ of insulation 1h, is warmed up to 880 ℃ of insulation 10min again; Cooling rate with 3 ℃/min cools to 400 ℃, cools to room temperature with the furnace, takes out print and carries out sanding and polishing, adopting agilent4991A to record specific inductivity is 64.8, dielectric loss is 0.0025, and temperature coefficient of resonance frequency 13ppm/ ℃, insulation resistance is 5.4 * 10
12Ω .cm.
Table 1 embodiment of the invention products obtained therefrom performance comparison
As known from Table 1, all samples all can be at middle low temperature (Ts≤900 ℃) sintering down; Specific inductivity 58～70@1MHz～the 3GHz of sample, dielectric loss are 0.001～0.003@1MHz～3GHz, resonance temperature factor τ
f=0 ± 15ppm/ ℃, insulation resistivity ρ is 2.2 * 10
12Ω .cm～5.8 * 10
13Ω .cm.
Claims (8)
1. the preparation method of a high-k low-temperature co-burning ceramic material, it is characterized in that: it may further comprise the 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 solvent and zirconia ball, adopted wet ball grinding 10～12 hours;
B. oven dry, pre-burning, broken step, it comprises the zirconia ball in the green powder precursor material that filters out behind the steps A ball milling, and in 100～120 ℃ of oven dry, 900 ± 20 ℃ of following pre-burnings, 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 the ZnO of glass powder precursor material according to 15～25 weight percents; The H of 75～85 weight percents
3BO
3Mix, add solvent and zirconia ball, adopted wet ball grinding 8～10 hours;
D. glass powder oven dry, fusion, broken step, it comprises the glass powder precursor material discharging behind C step ball milling is filtered out zirconia ball, in 100～120 ℃ of oven dry, at 1450 ± 50 ℃ of following melt water quenchings, 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; The high polymer binder aqueous solution that adds 5～15 weight percents then, ball milling is 4～6 hours again, mixes granulation, compressing tablet, binder removal sintering.
2. the preparation method of a kind of high-k low-temperature co-burning ceramic material as claimed in claim 1, it is characterized in that: the specific inductivity of described high-k low-temperature co-burning ceramic material is 58～70@1MHz～3GHz, dielectric loss is 0.001～0.003@1MHz～3GHz, f=0 ± 15ppm/ ℃ of resonance temperature factor τ, insulation resistivity ρ are 2.2 * 10
12Ω .cm～5.8 * 10
13Ω .cm.
3. the preparation method of a kind of high-k low-temperature co-burning ceramic material as claimed in claim 1, it is characterized in that: solvent described in described steps A, C, the E is deionized water or dehydrated alcohol; Described zirconia ball is Φ 3mm～5mm.
4. the preparation method of a kind of high-k low-temperature co-burning ceramic material as claimed in claim 1, it 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 high-k low-temperature co-burning ceramic material as claimed in claim 1, it is characterized in that: the weight proportion of the described glass powder precursor material of C step, solvent, zirconia ball is 1: 0.8～1: 2.
6. the preparation method of a kind of high-k low-temperature co-burning ceramic material as claimed in claim 1, it is characterized in that: the weight proportion of the described mixed powder of E step, solvent, zirconia ball is 1: 0.8～1: 2.
7. the preparation method of a kind of high-k low-temperature co-burning ceramic material as claimed in claim 1 is characterized in that: polyvinyl butyral acetal or polyvinyl alcohol water solution that the described high polymer binder aqueous solution of E step is 5～15 weight percents.
8. the preparation method of a kind of high-k low-temperature co-burning ceramic material as claimed in claim 1, it is characterized in that: the described binder removal sintering process of step e comprises ceramic plate is warmed up to 500 ℃ of insulation 1h with the heat-up rate of 2 ℃/min, be warmed up to 880 ℃ of insulation 10min again, cooling rate with 3 ℃/min cools to 400 ℃, cools to room temperature with the furnace.
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