CN102690118B - NP0 type ceramic capacitor dielectric material and its preparation method - Google Patents
NP0 type ceramic capacitor dielectric material and its preparation method Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 46
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 17
- 238000005245 sintering Methods 0.000 claims abstract description 65
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 36
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 30
- 238000001354 calcination Methods 0.000 claims description 23
- 239000000919 ceramic Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 229910000906 Bronze Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 239000010974 bronze Substances 0.000 claims description 5
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 18
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000007123 defense Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 61
- 239000010936 titanium Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 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
- 238000004364 calculation method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 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
- 230000000881 depressing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 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
- 239000004570 mortar (masonry) Substances 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
The invention discloses an NP0 type ceramic capacitor dielectric material. The material includes a BRT (Ba6-3x(R1yR21-y)8+2xTi18O54) main phase, a ZnB ((ZnO).(B2O3)n) sintering aid, a second main group compound and a component BiTi second phase that can be added or not. Specifically, the BiTi second phase accounts for 0-9wt% of the BRT main phase, the ZnB sintering aid accounts for 2-12wt% of the BRT main phase, and the second main group compound accounts for 0-18wt% of the BRT main phase and its dosage is not equal to 0. The material has a room-temperature dielectric constant up to 45-70, a room-temperature dielectric loss less than 0.05%, a temperature coefficient of capacitance not more than 27-33ppm/DEG C in a temperature range of -55-150DEG C, and room-temperature resistivity greater than 1012ohm.cm, thus being suitable for industrial production. With a high repetition rate, the NP0 type ceramic capacitor dielectric material provided in the invention is a high-performance and low-cost environment friendly dielectric ceramic material, and is widely applied in electronic communications, national defense and military industry, aerospace, exploration and other fields.
Description
Technical field
The present invention relates to be applied to the technical field of ceramic material of electronic devices and components, be specifically related to a kind of NP0 type ceramic capacitor dielectric material and preparation method with low-temperature sintering temperature stability.
Background technology
NP0 is a kind of the most frequently used I class ceramic condenser with temperature compensation characteristic, is one of electrical condenser that electrical capacity and dielectric loss are the most stable, and it is extensively suitable for the tank capacitance of vibrator, resonator and the coupling capacity in high frequency circuit.According to the international EIA of Electronic Industries Association USA (Electronic Industries Association) standard, NP0 temperature-stable electrical condenser refers to that take the capacitance of 25 ℃ is benchmark, in temperature within the scope of-55 ℃ to+150 ℃, temperature coefficient of capacitance (TCC)≤30ppm/ ℃ requires dielectric loss lower than 0.05% simultaneously.Adopting the NP0 characteristic stupalith of MLCC technology is by ceramic dielectic and metal electrode alternative stacked, burn altogether as a whole, it has, and volume is little, insulation resistance is high, parasitic inductance is low, plurality of advantages such as high frequency characteristics is good and enjoy favor, be particularly suitable for chip type surface mounting technology, can greatly improve circuit packing density, dwindle machine volume, thereby development is rapid in slice component.Although the cost of single electrical condenser is very low, hundreds of millions of usage quantitys allows it contain considerable economic worth.
Laminated ceramic capacitor is many at sintering in atmosphere, material sintering temperature is many more than 1000 ℃, the inner electrode using is metal Pd or Pd-Ag alloy substantially, but along with the continuous of Pd price risen, in part MLCC, the cost of electrode accounts for 70% of laminated ceramic capacitor production cost unexpectedly.For reducing production costs, use pure Ag metal just imperative as electrode in MLCC.But the fusing point of Ag metal is only 961.93 ℃, use the pure Ag inner electrode requirement sintering temperature can not be higher than 920 ℃, therefore MLCC material require of new generation maintains higher material property at low temperatures when densified sintering product.
The BaO-R with tungsten bronze(s) ore deposit structure
2o
3-TiO
2(R=rare earth element) as principal phase material, is one and has higher specific inductivity in the relatively ripe system of microwave regime application, be 80～120 under room temperature, and temperature factor is close to zero.Therefore this structure can not undergo phase transition below at 300 ℃, and what high and low temperature environment performance in actual applications all showed is very stable.Domestic patent CN100424038C adopts ZnB as sintering agent, the material of sintering NP0 standard at 910～970 ℃, but specific inductivity relatively low be 25～41; Domestic patent CN 100372802C adopts BaO-R
2o
3-TiO
2as principal phase material, by being necessarily entrained in 1100 ℃ of left and right sintering, go out to meet the MLCC material of the specific inductivity 50～60 of NP0 standard.Domestic patent CN1746132 adopts BaO-R
2o
3-TiO
2the microwave material specific inductivity of preparing as principal phase can reach 120, but sintering temperature requires more than 1220 ℃.
Summary of the invention
The object of this invention is to provide a kind of NP0 type ceramic capacitor dielectric material and preparation method thereof.
NP0 type ceramic capacitor dielectric material provided by the invention, comprises BRT principal phase, BiTi second-phase, ZnB sintering agent and the second main group compound;
Described BRT principal phase is the Ba of tungsten bronze(s) ore deposit structure
6-3x(R1
yr2
1-y)
8+2xti
18o
54shown in compound, described Ba
6-3x(R1
yr2
1-y)
8+2xti
18o
54in, 0.5≤x≤0.7, x specifically can be 0.6-0.7, and y specifically can be 0.2-0.5 or 0.2-0.3,0≤y≤1, R1 and R2 are all selected from least one in La, Eu, Sm, Nd, Pr, Ce and Dy;
Described ZnB sintering agent is (ZnO) (B
2o
3)
nshown in compound, described (ZnO) (B
2o
3)
nin, 0.7≤n≤0.9, n specifically can be 0.75-0.8;
Described the second main group compound is selected from SrCO
3, SrNO
3, CaO, CaCO
3, Ca (NO
3)
2, MgO, MgCO
3, Mg (NO
3)
2, (MgCO
3)
4mg (OH)
2, BaCO
3with at least one in BaO.
In the NP0 type ceramic capacitor dielectric material that the invention described above provides, also can comprise B component iTi second-phase; Described BiTi second-phase is (Bi
2o
3) (TiO
2)
nshown in compound, described (Bi
2o
3) (TiO
2)
nin, 1.4≤n≤1.6, n specifically can be 1.45-1.55,1.45-1.5 or 1.5-1.55.The NP0 type ceramic capacitor dielectric material that the invention described above provides also can only be comprised of said components.Wherein, described BiTi second-phase accounts for the 0-9% of described BRT principal phase weight, specifically can be 0-8%, 0-6%, 0-4%, 0-2%, 0-1%, 1-8%, 1-6%, 1-4%, 1-2%, 2-8%, 2-6%, 2-4%, 4-6%, 4-8% or 6-8%, preferably 1-8%, described ZnB sintering agent accounts for the 2-12% of described BRT principal phase weight, specifically can be 4-10%, 4-6% or 6-10%, described the second main group compound accounts for the 0-18% of described BRT principal phase weight, specifically can be 0.5-16%, 0.5-10%, 0.5-6%, 0.5-5%, 0.5-4%, 0.5-3%, 0.5-2%, 0.5-1%, 1-16%, 1-10%, 1-6%, 1-5%, 1-4%, 1-3%, 1-2%, 2-16%, 2-10%, 2-6%, 2-5%, 2-4%, 2-3%, 3-16%, 3-10%, 3-6%, 3-5%, 3-4%, 4-16%, 4-10%, 4-6%, 4-5%, 5-16%, 5-10%, 5-6%, 6-16%, 6-10% or 10-16%, the consumption of described the second main group compound is not 0.
Described BRT principal phase as one of component is to obtain according to the method preparation comprising the steps: by BaCO
3and TiO
2with in following rare earth oxide any two kinds according to described Ba
6-3x(R1
yr2
1-y)
8+2xti
18o
54shown in the mol ratio of Ba, Ti, R1 and R2 mix dry after calcining and obtaining: La
2o
3, Eu
2o
3, Sm
2o
3, Nd
2o
3, Pr
2o
3, Ce
2o
3and Dy
2o
3; This is prepared in the calcining step of described BRT principal phase method, and temperature is 1100～1200 ℃, and preferably 1150 ℃, the time is 1-4 hour, preferably 2 hours; This synthetic method is solid phase method.In actually operating, described " by BaCO
3and TiO
2with in following rare earth oxide at least two kinds according to described Ba
6-3x(R1
yr2
1-y)
8+2xti
18o
54shown in the mol ratio of Ba, Ti, R1 and R2 mix " in step, BaCO
3, TiO
2with the mol ratio of described rare earth oxide be (6-3x): (8+2x)/2: 18, the mol ratio of two kinds of rare earth oxides used is y: (1-y).
As adding the described BiTi second-phase that can not add component, be Bi
2o
3with TiO
2the auxiliary phase that solid solution forms, this BiTi second-phase is mainly used to improve specific inductivity, adjusts dielectric temperature coefficient, also has the effect that reduces sintering temperature simultaneously.This BiTi second-phase is to obtain according to the method preparation comprising the steps: by Bi
2o
3and Bi (NO
3)
3in at least one and TiO
2according to described (Bi
2o
3) (TiO
2)
nshown in the mol ratio of Bi and Ti mix dry after calcining and obtaining; This is prepared in the calcining step of described BiTi second-phase method, and temperature is 800-1000 ℃, and preferably 850 ℃, the time is 1-4 hour, preferably 2 hours;
As the described ZnB sintering agent of one of component, be mainly used in reducing the sintering temperature of material, contribute to control the grain-size of material; This ZnB sintering agent is to obtain according to the method preparation comprising the steps: by Zn (COOCH
3)
22H
2at least one in O and ZnO and H
3bO
3according to described (ZnO) (B
2o
3)
nthe mol ratio of middle Zn and B is calcined after mixing and drying and is obtained; This is prepared in the calcining step of described ZnB sintering agent method, and temperature is 500～700 ℃, and preferably 600 ℃, the time is 0.5-3 hour, preferably 1 hour.
As the second main group compound of one of component, can suppress the generation of dephasign, the dielectric loss of reduction material, contribute to improve specific inductivity simultaneously.
The method of the above-mentioned NP0 type of preparation provided by the invention ceramic capacitor dielectric material, comprises the steps:
1) described BRT principal phase, described BiTi second-phase, described ZnB sintering agent, described the second main group compound and water are mixed and carries out ball milling, oven dry obtains ceramic powder after sieving;
Or, described BRT principal phase, described BiTi second-phase, described ZnB sintering agent, described the second main group compound and water are mixed and carries out ball milling, oven dry obtains ceramic powder after sieving;
Described BRT principal phase is the Ba of tungsten bronze(s) ore deposit structure
6-3x(R1
yr2
1-y)
8+2xti
18o
54shown in compound, described Ba
6-3x(R1
yr2
1-y)
8+2xti
18o
54in, 0.5≤x≤0.7,0≤y≤1, R1 and R2 are all selected from least one in La, Eu, Sm, Nd, Pr, Ce and Dy;
Described ZnB sintering agent is (ZnO) (B
2o
3)
nshown in compound, described (ZnO) (B
2o
3)
nin, 0.7≤n≤0.9;
Described the second main group compound is all selected from SrCO
3, SrNO
3, CaO, CaCO
3, Ca (NO
3)
2, MgO, MgCO
3, Mg (NO
3)
2, (MgCO
3)
4mg (OH)
2, BaCO
3with at least one in BaO;
Described BiTi second-phase is (Bi
2o
3) (TiO
2)
nshown in compound, described (Bi
2o
3) (TiO
2)
nin, 1.4≤n≤1.6;
2) by described step 1) after gained ceramic powder compressing tablet, first the speed with 150～200 ℃/h is warmed up to 400～600 ℃, be incubated after 0.5～2 hour, after being warmed up to 900～920 ℃ with the speed of 200～300 ℃/h again, be incubated after 2～14 hours, naturally cool to room temperature, obtain described NP0 type ceramic capacitor dielectric material.
The described step 1 of aforesaid method) in, described BiTi second-phase accounts for the 0-9% of described BRT principal phase weight, specifically can be 0-8%, 0-6%, 0-4%, 0-2%, 0-1%, 1-8%, 1-6%, 1-4%, 1-2%, 2-8%, 2-6%, 2-4%, 4-6%, 4-8% or 6-8%, preferably 1-8%, described ZnB sintering agent accounts for the 2-12% of described BRT principal phase weight, specifically can be 4-10%, 4-6% or 6-10%, described the second main group compound accounts for the 0-18% of described BRT principal phase weight, specifically can be 0.5-16%, 0.5-10%, 0.5-6%, 0.5-5%, 0.5-4%, 0.5-3%, 0.5-2%, 0.5-1%, 1-16%, 1-10%, 1-6%, 1-5%, 1-4%, 1-3%, 1-2%, 2-16%, 2-10%, 2-6%, 2-5%, 2-4%, 2-3%, 3-16%, 3-10%, 3-6%, 3-5%, 3-4%, 4-16%, 4-10%, 4-6%, 4-5%, 5-16%, 5-10%, 5-6%, 6-16%, 6-10% or 10-16%, the consumption of described the second main group compound is not 0, the consumption of described water is the 50-300% of described BRT principal phase weight, preferably 150%, in described ball milling step, the time is 8-48 hour, and preferably 24 hours, temperature was 0-60 ℃, preferably 30 ℃, in described baking step, temperature is 70-140 ℃, and preferably 105 ℃, the time is 6-24 hour, preferably 12 hours, described sieving in step, the order number of sieve aperture is 80-200 order, preferably 120 orders.
Described step 2) in, described elder generation is warmed up to 400～600 ℃ with the speed of 150～200 ℃/h, be incubated in 0.5～2 hour step, temperature rise rate is preferably 200 ℃/h, be warming up in the step of 400-600 ℃, temperature is preferably 500 ℃, is incubated in 0.5-2 hour step, and soaking time is preferably 1 hour; Compressing tablet step is to carry out according to ordinary method, before compressing tablet, ceramic powder is mixed with organic adhesive so that compressing tablet, organic binder bond used is various conventional caking agents, as to can be mass percentage concentration be 5% PVOH (PVA) aqueous solution or polyvinylacetal (PVB) aqueous solution, and the consumption of this organic adhesive is all identical with existing method.
In addition, in the method, described BRT principal phase is to obtain according to the method preparation comprising the steps: by BaCO
3and TiO
2with in following rare earth oxide any two kinds according to described Ba
6-3x(R1
yr2
1-y)
8+2xti
18o
54shown in the mol ratio of Ba, Ti, R1 and R2 mix dry after calcining and obtaining: La
2o
3, Eu
2o
3, Sm
2o
3, Nd
2o
3, Pr
2o
3, Ce
2o
3and Dy
2o
3; In described calcining step, temperature is 1100～1200 ℃, and preferably 1150 ℃, the time is 1-4 hour, preferably 2 hours; In actually operating, described " by BaCO
3and TiO
2with in following rare earth oxide at least two kinds according to described Ba
6-3x(R1
yr2
1-y)
8+2xti
18o
54shown in the mol ratio of Ba, Ti, R1 and R2 mix " in step, BaCO
3, TiO
2with the mol ratio of described rare earth oxide be (6-3x): (8+2x)/2: 18, wherein the mol ratio of two kinds of rare earth oxides used is y: (1-y).
Described BiTi second-phase is to obtain according to the method preparation comprising the steps: by Bi
2o
3and Bi (NO
3)
3in at least one and TiO
2according to described (Bi
2o
3) (TiO
2)
nshown in the mol ratio of Bi and Ti mix dry after calcining and obtaining; In described calcining step, temperature is 800-1000 ℃, and preferably 850 ℃, the time is 1-4 hour, preferably 2 hours;
Described ZnB sintering agent is to obtain according to the method preparation comprising the steps: by Zn (COOCH
3)
22H
2at least one in O and ZnO and H
3bO
3according to described (ZnO) (B
2o
3)
nthe mol ratio of middle Zn and B be added to the water mix dry after calcining and obtaining; In described calcining step, temperature is 500～700 ℃, and preferably 600 ℃, the time is 0.5-3 hour, preferably 1 hour.
NP0 type ceramic capacitor dielectric material provided by the invention, preparation method's technique is simple, easy handling; The temperature stability of material is good, and specific inductivity is high, good reliability; The BiTi second-phase of introducing in the present invention's formula and the second main group compound can make ceramic temperature coefficient of capacitance (TCC) close to zero, more easily meet NP0 standard; Its room temperature dielectric constant can reach 45～70, and dielectric loss is less than 0.05%, be no more than ± 30ppm/ ℃ of temperature coefficient of capacitance in-55～150 ℃ of temperature ranges, room temperature resistivity > 10
12Ω cm; The ZnB sintering agent that the present invention introduces, can be reduced to the sintering temperature of stupalith below 920 ℃; The gained NP0 type stupalith environmentally harmful elements such as lead (Pb), arsenic (As), cadmium (Cd), mercury (Hg), chromium (Cr) that undope, be applicable to industrial production, repetition rate is high, be the environment-friendly type dielectric ceramic material of a high-performance and low-cost, in application such as telecommunications, defence and military, aerospace and Exploration Domain, have a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the XRD spectral line comparison of preparing the ceramic plate of gained NP0 type ceramic capacitor dielectric material sample 1～4 after 900 ℃ of sintering in embodiment 1;
Fig. 2 is the dielectric constant with temperature change curve of preparing the ceramic plate of gained NP0 type ceramic capacitor dielectric material sample 6,7,8 and 10 after 900 ℃ of sintering in embodiment 2;
Fig. 3 is the surperficial microstructure of preparing the ceramic plate of gained NP0 type ceramic capacitor dielectric material sample 8 after 900 ℃ of sintering in embodiment 2;
Fig. 4 is the surperficial microstructure of preparing the ceramic plate of gained NP0 type ceramic capacitor dielectric material sample 12 after 900 ℃ of sintering in embodiment 3;
Fig. 5 is the surperficial microstructure of preparing the ceramic plate of gained NP0 type ceramic capacitor dielectric material sample 17 after 900 ℃ of sintering in embodiment 4;
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.Described testing method if no special instructions, is ordinary method.
Embodiment 1
1) adopting solid phase method to prepare component is Ba
6-3x(Nd
ysm
1-y)
8+2xti
18o
54the BRT principal phase of (x=0.6, y=0.3): by analytically pure barium carbonate, Samarium trioxide, Neodymium trioxide and titanium dioxide according to Ba
6-3x(Nd
ysm
1-y)
8+2xti
18o
54the mol ratio of Ba, Ti, Nd and Sm in (x=0.6, y=0.3), weighs 48 hours batch mixings of ball milling after above-mentioned four kinds of compounds, dries, and then, 1150 ℃ of calcinings 2 hours, obtains BRT principal phase;
Preparation component is (Bi
2o
3) (TiO
2)
1.45biTi second-phase: by analytically pure bismuthous oxide bismuth trioxide and titanium dioxide according to (Bi
2o
3) (TiO
2)
1.45the mol ratio of middle Bi and Ti is 2: 1.45, weighs 36 hours batch mixings of ball milling after above-mentioned bismuthous oxide bismuth trioxide and titanium dioxide, dries, and then, 850 ℃ of calcinings 2 hours, obtains BiTi second-phase;
Preparation component is (ZnO) (B
2o
3)
0.8znB sintering agent: by boric acid and zinc acetate according to (ZnO) (B
2o
3)
0.8the mol ratio of middle Zn and B is 1: 0.6, weighs after above-mentioned boric acid and zinc acetate heated and stirred in water and, to dissolving completely, then dries, and 600 ℃ of calcinings 1 hour, obtains ZnB sintering agent;
2) prepare NP0 type ceramic capacitor dielectric material: by step 1) gained BRT principal phase, BiTi second-phase (Bi
2o
3) (TiO
2)
1.45, the second main group compound S rCO
3according to weight ratio, be 100: 8: 0.5, ZnB sintering agent (ZnO) (B
2o
3)
0.8be followed successively by 2: 100 with the weight ratio of BRT principal phase, 4: 100,6: 100 and 10: 100 (as shown in table 1) weigh, by load weighted powder ZrO
2ball is as ball-milling medium, deionized water is 150 times of dispersion agent (consumption of this deionized water is step 1) gained BRT principal phase quality), ball milling was poured out after 24 hours, with electrically heated drying cabinet, at 105 ℃, dried after 12 hours, with 120 order sieve, obtain ceramic powder, get gained ceramic powder and put into agate mortar, add the PVA solution that 2～3 mass percentage concentration are 5%, after mixing, at 2MPa pressure, depressing to diameter is 10mm, thickness is the disc-shaped green compact of 1mm, carry out again sintering, in sintering process, first the speed with 200 ℃/h is warmed up to 500 ℃, be incubated and within 1 hour, carry out the organic binder bond PVA solution that binder removal is added to remove, and then be warmed up to 900 ℃ with the speed of 300 ℃/h, be incubated 10 hours, after completing, last sintering procedure naturally cools to room temperature with stove, obtain NP0 type ceramic capacitor dielectric material sample 1～4 provided by the invention.
Upper silver electrode is burnt respectively in the both sides of NP0 type ceramic capacitor dielectric material sample 1-4 after above-mentioned sintering, make wafer capacitance device, then test also relative permittivity, loss tangent and the temperature coefficient of capacitance of calculation sample, test frequency 1MHz, test voltage 1Vrms, Range of measuring temp-55～150 ℃.The performance of gained NP0 type ceramic capacitor dielectric material sample 1-4 is as shown in table 1, and wherein, temperature coefficient of capacitance (TCC) is defined as follows: TCCppm/ ℃=10
6* (ε
(T)-ε
(25 ℃))/((T-25) * ε
(25 ℃)).
The performance list of the addition of table 1, ZnB sintering agent and gained NP0 type ceramic capacitor dielectric material sample
As shown in Table 1, the specific inductivity of sample 1～4 is 61～67, and temperature coefficient of capacitance is in the scope of-3～14ppm/ ℃, and room temperature resistivity is 10
13Ω cm left and right.From the compactness of material, only have when sintering agent content is during higher than 4wt%, material could densified sintering product.But the increase of sintering agent can impel the generation of low-activation energy dephasign, cause the rising of dielectric loss, so the dielectric loss of sample 1～4 is 0.1～-0.2%.Fig. 1 is the XRD spectral line of sample, can find out the increase along with sintering agent content, and the intensity at dephasign peak is increasing, thereby content is also increasing, and conforms to analysis before.
Embodiment 2
According to preparing NP0 type ceramic capacitor dielectric material sample 5～10 with the identical method of embodiment 1, only BRT principal phase composition is replaced with to Ba
6-3x(Nd
ysm
1-y)
8+2xti
18o
54(x=0.7, y=0.5), the weight ratio of ZnB sintering agent and BRT principal phase replaces with 4: 100, and the weight ratio of BiTi second-phase and BRT principal phase replaces with 4: 100, the second main group compound S rCO
3with the weight ratio of BRT principal phase according to replacing with successively 1: 100 shown in table 2,2: 100,4: 100,6: 100,10: 100 and 16: 100, obtain NP0 type ceramic capacitor dielectric material sample 5～10 provided by the invention, composition and the performance of gained sample 5-10 are as shown in table 2.
The performance list of the addition of table 2, the second main group compound and gained NP0 type ceramic capacitor dielectric material sample
In sample, add SrCO
3afterwards, dielectric loss is effectively reduced, and when doping content is during at 2～6wt%, dielectric loss can remain on below 0.05%.What Fig. 2 showed is the dielectric constant with temperature change curve of 5,6,7 and 10 4 samples.Along with SrCO
3the increase of content, specific inductivity presents the phenomenon of falling after rising, and this is identical with the rule under normal temperature.The reduction of sample 10 specific inductivity be too much Sr element hindered sintering agent help burning effect, cause that material sintering is not fine and close to be caused.Sample 6～8 not only loss is low, and insulation resistance is 1 * 10
13about Ω cm, and temperature coefficient of capacitance is all within ± 30ppm/ ℃, has reached the standard of NP0.Wherein the performance of sample 8 is better, and specific inductivity reaches 70.Fig. 3 is the surface microscopic topographic of sample 8, as seen from the figure, the uniform crystal particles of this sample 8, bar-like grains is few.
Embodiment 3
According to preparing NP0 type ceramic capacitor dielectric material sample 11～14 with the identical method of embodiment 1, only BRT principal phase component is replaced with to Ba
6-3x(La
ysm
1-y)
8+2xti
18o
54(x=0.7, y=0.2), the component of ZnB sintering agent replaces with (ZnO) (B
2o
3)
0.75, the weight ratio of this ZnB sintering agent and BRT principal phase replaces with 6: 100, and the weight ratio of BiTi second-phase and BRT principal phase replaces with 4: 100, and the second main group compound replaces with CaCO
3the weight ratio of itself and BRT principal phase according to replacing with successively 1: 100 shown in table 3,3: 100,6: 100 and 10: 100, in sintering step " speed with 300 ℃/h is warmed up to 900 ℃ again; be incubated 10 hours ", soaking time is replaced with to 6 hours, obtain NP0 type ceramic capacitor dielectric material sample 11～14 provided by the invention, composition and the performance of gained sample 11～14 are as shown in table 3.
The performance list of the addition of table 3, the second main group compound and gained NP0 type ceramic capacitor dielectric material sample
As shown in Table 3, use CaCO instead
3after, a small amount of doping still can be played the effect that reduces dielectric loss, but excessive doping can cause density to reduce, and properties all suffers damage.Sample 11～12 can both meet the standard of NP0, specific inductivity 58～65, and room temperature dielectric loss is lower than 0.04%, and temperature coefficient of capacitance is in ± 30ppm/ ℃.The surface topography of sample 12 is shown in Fig. 4, compares with the sample of the Sr that adulterates in embodiment 2, and the length-to-diameter ratio of bar-like grains increases.
Embodiment 4
According to preparing NP0 type ceramic capacitor dielectric material sample 15～18 with the identical method of embodiment 2, only the composition of BiTi second-phase is replaced with to (Bi
2o
3) (TiO
2)
1.55the second main group compound replaces with MgO, the weight ratio of this second main group compound and BRT principal phase according to replacing with successively 0.5: 100 shown in table 4,1: 100,2: 100,5: 100, in sintering step " speed with 300 ℃/h is warmed up to 900 ℃ again; be incubated 10 hours ", soaking time is replaced with to 6 hours, obtain NP0 type ceramic capacitor dielectric material sample 15～18 provided by the invention.Composition and the performance of gained sample 15～18 are as shown in table 4.
The performance list of the addition of table 4, the second main group compound and gained NP0 type ceramic capacitor dielectric material sample
As shown in Table 4, the sample specific inductivity of employing MgO doping is relatively low is 42～47, and dielectric loss is all below 0.03%, and the sample 17～18 that doping content is higher meets NP0 standard.Lower from doping effect specific inductivity, because Mg element mainly rests on grain surface, grain growing is played to inhibition, cause sample density to reduce.From the microstructure of Fig. 5 sample 16, in microscopic appearance, bar-like grains is few, crystal grain is more even simultaneously.
Embodiment 5
According to preparing NP0 type ceramic capacitor dielectric material sample 19～23 with the identical method of embodiment 1, only the weight ratio of ZnB sintering agent and BRT principal phase is replaced with to 4: 100, the composition of BiTi second-phase replaces with (Bi
2o
3) (TiO
2)
1.5the weight ratio of this BiTi second-phase and BRT principal phase according to replacing with successively 0: 100 shown in table 5,1: 100,2: 100,4: 100,6: 100, in sintering step " speed with 300 ℃/h is warmed up to 900 ℃ again; be incubated 10 hours ", soaking time is replaced with to 12 hours, obtain NP0 type ceramic capacitor dielectric material sample 19～23 provided by the invention.Composition and the performance of gained sample 19～23 are as shown in table 4.
The performance list of the addition of table 4, BiTi second-phase and gained NP0 type ceramic capacitor dielectric material sample
As shown in Table 5, the addition that reduces BiTi second-phase can reduce dielectric loss, and specific inductivity also can reduce simultaneously.The less sample 19～22 of doping content meets NP0 standard.BiTi second-phase also has certain sintering aids role, can improve ceramic density.
Claims (10)
1. a NP0 type ceramic capacitor dielectric material, comprises BRT principal phase, ZnB sintering agent and the second main group compound;
Described BRT principal phase is the Ba of tungsten bronze(s) ore deposit structure
6-3x(R1
yr2
1-y)
8+2xti
18o
54shown in compound, described Ba
6-3x(R1
yr2
1-y)
8+2xti
18o
54in, 0.5≤x≤0.7,0≤y≤1, R1 and R2 are all selected from least one in La, Eu, Sm, Nd, Pr, Ce and Dy;
Described ZnB sintering agent is (ZnO) (B
2o
3)
nshown in compound, described (ZnO) (B
2o
3)
nin, 0.7≤n≤0.9;
Described the second main group compound is selected from SrCO
3, SrNO
3, CaO, CaCO
3, Ca (NO
3)
2, MgO, MgCO
3, Mg (NO
3)
2, (MgCO
3)
4mg (OH)
2, BaCO
3with at least one in BaO;
Wherein, described ZnB sintering agent accounts for the 4-6% of described BRT principal phase weight, and described the second main group compound accounts for the 0.5-6% of described BRT principal phase weight.
2. dielectric material according to claim 1, is characterized in that: described NP0 type ceramic capacitor dielectric material is comprised of described BRT principal phase, described ZnB sintering agent and described the second main group compound.
3. dielectric material according to claim 1, is characterized in that: described NP0 type ceramic capacitor dielectric material also comprises B component iTi second-phase; Described BiTi second-phase is (Bi
2o
3) (TiO
2)
nshown in compound, described (Bi
2o
3) (TiO
2)
nin, 1.4≤n≤1.6.
4. dielectric material according to claim 3, is characterized in that: described NP0 type ceramic capacitor dielectric material is comprised of described BRT principal phase, described BiTi second-phase, described ZnB sintering agent and described the second main group compound; Wherein, described BiTi second-phase accounts for the 0-4% of described BRT principal phase weight, and described ZnB sintering agent accounts for the 4-6% of described BRT principal phase weight, and described the second main group compound accounts for the 0.5-6% of described BRT principal phase weight, and the consumption of described BiTi second-phase is not 0.
5. according to the arbitrary described dielectric material of claim 1-4, it is characterized in that: described BRT principal phase is to obtain according to the method preparation comprising the steps: by BaCO
3and TiO
2with in following rare earth oxide any two kinds according to described Ba
6-3x(R1
yr2
1-y)
8+2xti
18o
54shown in the mol ratio of Ba, Ti, R1 and R2 mix dry after calcining and obtaining: La
2o
3, Eu
2o
3, Sm
2o
3, Nd
2o
3, Pr
2o
3, Ce
2o
3and Dy
2o
3;
Described BiTi second-phase is to obtain according to the method preparation comprising the steps: by Bi
2o
3and Bi (NO
3)
3in at least one and TiO
2according to described (Bi
2o
3) (TiO
2)
nshown in the mol ratio of Bi and Ti mix dry after calcining and obtaining;
Described ZnB sintering agent is to obtain according to the method preparation comprising the steps: by Zn (COOCH
3)
22H
2at least one in O and ZnO and H
3bO
3according to described (ZnO) (B
2o
3)
nthe mol ratio of middle Zn and B be added to the water mix dry after calcining and obtaining.
6. dielectric material according to claim 5, is characterized in that: prepare in the calcining step of described BRT principal phase method, temperature is 1100～1200 ℃, and the time is 1-4 hour;
Prepare in the calcining step of described BiTi second-phase method, temperature is 800-1000 ℃, and the time is 1-4 hour;
Prepare in the calcining step of described ZnB sintering agent method, temperature is 500～700 ℃, and the time is 0.5-3 hour.
7. dielectric material according to claim 6, is characterized in that: prepare in the calcining step of described BRT principal phase method, temperature is 1150 ℃, and the time is 2 hours;
Prepare in the calcining step of described BiTi second-phase method, temperature is 850 ℃, and the time is 2 hours;
Prepare in the calcining step of described ZnB sintering agent method, temperature is 600 ℃, and the time is 1 hour.
8. a method of preparing the arbitrary described NP0 type ceramic capacitor dielectric material of claim 1-7, comprises the steps:
1) described BRT principal phase, described ZnB sintering agent, described the second main group compound and water are mixed and carries out ball milling, oven dry obtains ceramic powder after sieving;
Or, described BRT principal phase, described BiTi second-phase, described ZnB sintering agent, described the second main group compound and water are mixed and carries out ball milling, oven dry obtains ceramic powder after sieving;
Described BRT principal phase is the Ba of tungsten bronze(s) ore deposit structure
6-3x(R1
yr2
1-y)
8+2xti
18o
54shown in compound, described Ba
6-3x(R1
yr2
1-y)
8+2xti
18o
54in, 0.5≤x≤0.7,0≤y≤1, R1 and R2 are all selected from least one in La, Eu, Sm, Nd, Pr, Ce and Dy;
Described ZnB sintering agent is (ZnO) (B
2o
3)
nshown in compound, described (ZnO) (B
2o
3)
nin, 0.7≤n≤0.9;
Described the second main group compound is all selected from SrCO
3, SrNO
3, CaO, CaCO
3, Ca (NO
3)
2, MgO, MgCO
3, Mg (NO
3)
2, (MgCO
3)
4mg (OH)
2, BaCO
3with at least one in BaO;
Described BiTi second-phase is (Bi
2o
3) (TiO
2)
nshown in compound, described (Bi
2o
3) (TiO
2)
nin, 1.4≤n≤1.6;
2) by after described step 1) gained ceramic powder compressing tablet, first the speed with 150～200 ℃/h is warmed up to 400～600 ℃, be incubated after 0.5～2 hour, speed with 200～300 ℃/h was warmed up to 900～920 ℃ of insulations after 2～14 hours again, naturally cool to room temperature, obtain the arbitrary described NP0 type ceramic capacitor dielectric material of claim 1-7;
In described step 1), described BiTi second-phase accounts for the 0-4% of described BRT principal phase weight, and described ZnB sintering agent accounts for the 4-6% of described BRT principal phase weight, and described the second main group compound accounts for the 0.5-6% of described BRT principal phase weight; The consumption of described water is the 50-300% of described BRT principal phase weight.
9. method according to claim 8, is characterized in that: in described step 1) ball milling step, the time is 8-48 hour, and temperature is 0-60 ℃; In described baking step, temperature is 70-140 ℃, and the time is 6-24 hour; Described sieving in step, the order number of sieve aperture is 80-200 order.
10. method according to claim 9, is characterized in that: in described step 1) ball milling step, the time is 24 hours, and temperature is 30 ℃; In described baking step, temperature is 105 ℃, and the time is 12 hours; Described sieving in step, the order number of sieve aperture is 120 orders.
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| CN104402438B (en) * | 2014-11-21 | 2016-04-06 | 桂林理工大学 | Temperature-stable ultralow dielectric microwave dielectric ceramic Ca 2laBO 5 |
| CN108264348A (en) * | 2018-01-30 | 2018-07-10 | 华中科技大学 | A kind of high dielectric constant low loss microwave dielectric ceramics and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
-
2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
Non-Patent Citations (2)
| Title |
|---|
| Microwave dielectric and elastic properties of glass-added Ba6-3xR8+2xTi18O54 (x=2/3);N. Santha et al.;《Materials Chemistry and Physics》;20061231;第100卷;第423页左栏第1段 * |
| N. Santha et al..Microwave dielectric and elastic properties of glass-added Ba6-3xR8+2xTi18O54 (x=2/3).《Materials Chemistry and Physics》.2006,第100卷第423页左栏第1段. |
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