CN103524127B - High-frequency grain boundary layer ceramic capacitor medium and preparation method - Google Patents
High-frequency grain boundary layer ceramic capacitor medium and preparation method Download PDFInfo
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- CN103524127B CN103524127B CN201310462413.7A CN201310462413A CN103524127B CN 103524127 B CN103524127 B CN 103524127B CN 201310462413 A CN201310462413 A CN 201310462413A CN 103524127 B CN103524127 B CN 103524127B
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Abstract
The invention relates to the technical field of inorganic non-metallic materials, and especially relates to a high-frequency grain boundary layer ceramic capacitor medium and a preparation method. The ingredients of the formula comprise, by weight, 88-96% of (Sr0.96Ba0.04)TiO3, 0.1-3% of Ba(Li1/4Nb3/4)O3, 0.1-4% of Dy2O3, 0.1-2.0% of SiO2, 0.1-2.5% of Al2O3, 0.03-2.0% of SrCO3, 0.1-2.0% of ZnO-Li2O-Bi2O3 glass powder (ZLB) and 0.01-2% of CuO. The high-frequency grain boundary layer ceramic capacitor medium without lead or cadmium is prepared and obtained through a conventional preparation method for a ceramic capacitor medium and a one-time sintering process method by utilization of common chemical raw materials of capacitor ceramics, and the sintering temperature of the capacitor ceramics can be lowered. The medium is suitable for preparation of single-sheet ceramic capacitors and single-layer sheet-type ceramic capacitors.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, refer in particular to a kind of High-frequency grain boundary layer ceramic capacitor medium and preparation method thereof, it adopts conventional ceramic capacitor dielectric preparation method and once sintered processing method, utilize condenser ceramics general chemistry raw material, prepare unleaded, without the High-frequency grain boundary layer ceramic capacitor medium of cadmium, the sintering temperature of condenser ceramics can also be reduced, this medium is suitable for preparing monolithic ceramic capacitor and individual layer chip ceramic capacitor, greatly can reduce the cost of ceramic condenser, this dielectric permittivity is higher, easily realize the miniaturization of ceramic condenser, and good temp characteristic, simultaneously can improve proof voltage and dispersion frequency is high with the range of application expanding boundary ceramics electrical condenser, and it is free from environmental pollution in preparation and use procedure, security is high.
Background technology
Along with developing rapidly with universal of surface mounting technique, surface mount component (SMC) occupation rate in the electronic device steadily improves, 1997, World Developed Countries electronic devices and components chip rate reached more than 70%, the whole world average more than 40%, 2000, and whole world electronic devices and components chip rate reaches 70%, 2002, and chip rate is more than 85%, especially adapt to the national defence such as message area and aerospace leading-edge field to small-size multifunction electronics device urgent need day by day, comply with the portability of command, control, communications, and information terminal, miniaturization and multifunction trend, electronic element enters the all-round developing new period, individual layer chip semiconductor ceramic material is divided into surperficial stratotype and grain boundary layer type two class, is characterized in that volume is little, capacity is large, and in addition, intergranular semiconductor stupalith also has that good temp characteristic, frequency response characteristic are good, operating frequency advantages of higher, at present in the world, only have AVX, JOHANSON etc. can provide individual layer chip semiconductor ceramic material less than ten companies, the global market aggregate demand to individual layer chip semiconductor ceramic material element is up to 4,500,000,000/year, for adapting to an urgent demand day by day of electronic devices and components microminiaturizations, lightness, Composite, high frequency and high performance, semiconductor ceramic material is in miniaturization, high-k, high precision int and high frequency aspect are developed rapidly, and individual layer chip semiconductor ceramic material is the trend of development, the sintering temperature of general monolithic grain boundary layer ceramic capacitor medium and individual layer chip grain boundary layer ceramic capacitor medium is 1350 ~ 1430 DEG C, there are the following problems simultaneously: otherwise withstand voltage lower, temperature factor is larger, specific inductivity is lower, sintering process is all adopt double sintering method, that is: first high temperature reduction substantially, then applies insulation oxide and carries out oxidizing thermal treatment in middle temperature, technique is more complicated, and cost is higher, some adopts cladding process, and technique is more complicated, and costly, cost is also higher for raw material, and grain boundary layer ceramic capacitor medium sintering temperature of the present invention is about 1270 ~ 1290 DEG C, adopt once sintered technique (first binder removal before 500 DEG C in nitrogen simultaneously, then after higher than 1000 DEG C with heat up at a slow speed (30 ~ 50 DEG C/h), then in 1270 ~ 1290 DEG C of insulations, 3 ~ 5 hours sintering, be then slowly cooled to about 900 ~ 950 DEG C in air, be incubated process in 2 ~ 3 hours, last furnace cooling), greatly can reduce the cost of boundary ceramics electrical condenser like this, the simultaneously not leaded and cadmium of this patent capacitor ceramic dielectric, condenser ceramics is free from environmental pollution in preparation and use procedure, in addition, the specific inductivity of condenser ceramics of the present invention is high, can improve the capacity of ceramic condenser like this and miniaturization, meet the development trend of ceramic condenser, equally also can reduce the cost of ceramic condenser, grain boundary layer ceramic capacitor medium proof voltage of the present invention is high, dispersion frequency is high, holds use range and security that requirement etc. that temperature characteristics meets X7R is conducive to expanding boundary ceramics electrical condenser.
Summary of the invention
The object of this invention is to provide a kind of High-frequency grain boundary layer ceramic capacitor medium.
The object of the present invention is achieved like this:
High-frequency grain boundary layer ceramic capacitor medium formula composition comprises (weight percent): (Sr
0.96ba
0.04) TiO
388-96%, Ba (Li
1/4nb
3/4) O
30.1-3%, Dy
2o
30.1-4%, SiO
20.1-2.0%, Al
2o
30.1-2.5%, SrCO
30.03-2.0%, ZnO-Li
2o-Bi
2o
3glass powder (ZLB) 0.1-2.0%, CuO0.01-2%; Wherein (Sr
0.96ba
0.04) TiO
3, Ba (Li
1/4nb
3/4) O
3and ZnO-Li
2o-Bi
2o
3glass powder is adopt conventional chemical feedstocks with Solid phase synthesis respectively.
(Sr used in medium of the present invention
0.96ba
0.04) TiO
3following technique is adopted to prepare: by the chemical feedstocks SrCO of routine
3and BaCO
3and TiO
2by 0.96:0.04:1 molar ratio ingredient, put into alumina crucible after ground and mixed is even in 1250 ~ 1280 DEG C of insulations 120 minutes, solid state reaction kinetics (Sr
0.96ba
0.04) TiO
3, ground 200 mesh sieves after cooling, for subsequent use.
Ba (Li used in medium of the present invention
1/4nb
3/4) O
3following technique is adopted to prepare: by the chemical feedstocks BaCO of routine
3and Li
2cO
3and Nb
2o
5by 1:1/8:3/8 molar ratio ingredient, put into alumina crucible after ground and mixed is even in 700 DEG C of insulations 120 minutes, solid state reaction kinetics Ba (Li
1/4nb
3/4) O
3, ground 200 mesh sieves after cooling, for subsequent use.
ZnO-Li used in medium of the present invention
2o-Bi
2o
3glass powder (ZLB) adopts following technique to prepare: by chemical feedstocks ZnO and Li of routine
2cO
3and Bi
2o
3by 1:0.5:0.5 molar ratio ingredient, put into alumina crucible after ground and mixed is even in 600-650 DEG C of insulation 120 minutes, then quenching in water, obtains ZnO-Li after cooling
2o-Bi
2o
3glass powder, ground 200 mesh sieves, for subsequent use.
The present invention adopts following high frequency boundary ceramics medium preparation technology: first adopt conventional chemical feedstocks solid phase method to synthesize (Sr respectively
0.96ba
0.04) TiO
3, Ba (Li
1/4nb
3/4) O
3, ZnO-Li
2o-Bi
2o
3glass powder, then by formula batching, admixtion ball mill pulverizing is mixed, after drying, add tackiness agent granulation, be pressed into green sheet again, then binder removal and sintering (first binder removal before 500 DEG C in nitrogen is carried out in atmosphere, then after higher than 1000 DEG C with heat up at a slow speed (30 ~ 50 DEG C/h), then in 1270 ~ 1290 DEG C of insulations, 3 ~ 5 hours sintering, be then slowly cooled to 900 ~ 950 DEG C in air, be incubated process in 2 ~ 3 hours, last furnace cooling), obtain High-frequency grain boundary layer ceramic capacitor medium, by electrode on medium.
Described dielectric withstanding voltage is higher, and direct current proof voltage is 6.2-6.9kV/mm; Specific inductivity is high, is 30103-31515; Dispersion frequency (f
m) be 2.1-2.8GHz; Dielectric loss is 78-86 × 10
-4; Percentage of capacitance variation with temperature is little, meets the requirement of X7R characteristic; Insulation resistance is 70-85 × 10
10Ω cm.
The formula of above-mentioned ceramic dielectic preferably adopts following two kinds of schemes (weight percent):
(Sr
0.96ba
0.04) TiO
389-94%, Ba (Li
1/4nb
3/4) O
30.3-2.5%, Dy
2o
30.3-3.5%, SiO
20.1-1.5%, Al
2o
30.1-2%, SrCO
30.05-1.6%, ZnO-Li
2o-Bi
2o
3glass powder (ZLB) 0.2-1.8%, CuO0.06-2%;
(Sr
0.96ba
0.04) TiO
390-94%, Ba (Li
1/4nb
3/4) O
30.3-2.0%, Dy
2o
30.3-2.8%, SiO
20.1-1.3%, Al
2o
30.1-1.6%, SrCO
30.08-1.5%, ZnO-Li
2o-Bi
2o
3glass powder (ZLB) 0.3-1.5%, CuO0.1-1.8%.
Compared with prior art, tool has the following advantages in the present invention:
1, the medium of this patent adopts following once sintered technique: first binder removal before 500 DEG C in nitrogen, then after higher than 1000 DEG C with heat up at a slow speed (30 ~ 50 DEG C/h), then in 1270 ~ 1290 DEG C of insulations 3-5 hour sintering, be then slowly cooled to 900 ~ 950 DEG C and in air, be incubated process in 2 ~ 3 hours, last furnace cooling; Greatly can reduce the cost of ceramic condenser like this, not leaded and cadmium in the media components of this patent, environmentally safe.
2, the specific inductivity of this medium is high, is more than 30000; Proof voltage is high, and direct current proof voltage can reach more than 6kV/mm; Dielectric loss is little, is less than 1.0%; Dispersion frequency (f
m) high, dispersion frequency (f
m) up to more than 2GHz; The specific inductivity of this medium is high, can realize miniaturization and the Large Copacity of ceramic condenser, can reduce costs equally.
3, the temperature factor of this medium is low, and percentage of capacitance variation with temperature is little, meets the requirement of X7R characteristic; Dielectric loss is less than 1.0%, and in use procedure, stability is good, and security is high.
4, main raw material employing ceramic condenser level is pure can produce ceramic dielectic of the present invention.
5, this medium adopts conventional solid phase method ceramic capacitor dielectric preparation technology and a reduction-oxidation sintering process to be prepared.
Embodiment
Now the invention will be further described in conjunction with the embodiments, and table 1 provides the formula of embodiments of the invention totally 4 samples.
The main raw material of the embodiments of the invention formula of totally 4 samples adopts ceramic condenser level pure raw material, first adopts conventional chemical feedstocks solid phase method to synthesize (Sr respectively in the preparation
0.96ba
0.04) TiO
3, Ba (Li
1/4nb
3/4) O
3and ZnO-Li
2o-Bi
2o
3glass powder, then by above-mentioned formula batching, the material distilled water prepared or deionized water are adopted the mixing of planetary ball mill ball milling, material: ball: water=1:3:(0.6 ~ 1.0) (mass ratio), ball milling is after 4 ~ 8 hours, dry to obtain dry mash, in dry mash, add the concentration accounting for its weight 8 ~ 10% is the polyvinyl alcohol solution of 10wt%, carry out granulation, mixed rear mistake 40 mesh sieve, under 20 ~ 30Mpa pressure, carry out dry-pressing again become green sheet, first binder removal before 500 DEG C in nitrogen, then after higher than 1000 DEG C with heat up at a slow speed (30 ~ 50 DEG C/h), then in 1270 ~ 1290 DEG C of insulations, 3 ~ 5 hours sintering, then be cooled to 900 ~ 950 DEG C in air, be incubated process in 2 ~ 3 hours, last furnace cooling, at 780 ~ 800 DEG C, insulation carries out silver ink firing in 15 minutes again, form silver electrode, solder taul again, encapsulate, obtain boundary ceramics electrical condenser, test its dielectric properties.
The dielectric properties of above-mentioned each formula sample list in table 2, and condenser ceramics proof voltage prepared is as can be seen from Table 2 higher, and direct current proof voltage can reach more than 6kV/mm; Specific inductivity is high, is more than 30000; Dispersion frequency (f
m) up to more than 2GHz; Dielectric loss is less than 1.0 %; Percentage of capacitance variation with temperature is little, meets the requirement of X7R characteristic.
The formula of table 1 embodiments of the invention totally 4 samples
The dielectric properties of table 2 each formula sample
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a High-frequency grain boundary layer ceramic capacitor medium, it is characterized in that described medium composition calculates according to weight percent is: (Sr
0.96ba
0.04) TiO
388-96%, Ba (Li
1/4nb
3/4) O
30.1-3%, Dy
2o
30.1-4%, SiO
20.1-2.0%, Al
2o
30.1-2.5%, SrCO
30.03-2.0%, ZnO-Li
2o-Bi
2o
3glass powder 0.1-2.0%, CuO0.01-2%; Wherein (Sr
0.96ba
0.04) TiO
3, Ba (Li
1/4nb
3/4) O
3and ZnO-Li
2o-Bi
2o
3glass powder is adopt conventional chemical feedstocks with Solid phase synthesis respectively.
2. a kind of High-frequency grain boundary layer ceramic capacitor medium as claimed in claim 1, is characterized in that: described dielectric withstanding voltage is higher, direct current proof voltage is 6.2-6.9kV/mm; Specific inductivity is high, is 30103-31515; Dispersion frequency (f
m) be 2.1-2.8GHz; Dielectric loss is 78-86 × 10
-4; Percentage of capacitance variation with temperature is little, meets the requirement of X7R characteristic; Insulation resistance is 70-85 × 10
10Ω cm.
3. a kind of High-frequency grain boundary layer ceramic capacitor medium as claimed in claim 1, is characterized in that: described (Sr
0.96ba
0.04) TiO
3following technique is adopted to prepare: by the chemical feedstocks SrCO of routine
3and BaCO
3and TiO
2by 0.96:0.04:1 molar ratio ingredient, put into alumina crucible after ground and mixed is even in 1250 ~ 1280 DEG C of insulations 120 minutes, solid state reaction kinetics (Sr
0.96ba
0.04) TiO
3, ground 200 mesh sieves after cooling, for subsequent use.
4. a kind of High-frequency grain boundary layer ceramic capacitor medium as claimed in claim 1, is characterized in that: described Ba (Li
1/4nb
3/4) O
3following technique is adopted to prepare: by the chemical feedstocks BaCO of routine
3and Li
2cO
3and Nb
2o
5by 1:1/8:3/8 molar ratio ingredient, put into alumina crucible after ground and mixed is even in 700 DEG C of insulations 120 minutes, solid state reaction kinetics Ba (Li
1/4nb
3/4) O
3, ground 200 mesh sieves after cooling, for subsequent use.
5. a kind of High-frequency grain boundary layer ceramic capacitor medium as claimed in claim 1, is characterized in that: described ZnO-Li
2o-Bi
2o
3glass powder adopts following technique to prepare: by chemical feedstocks ZnO and Li of routine
2cO
3and Bi
2o
3by 1:0.5:0.5 molar ratio ingredient, put into alumina crucible after ground and mixed is even in 600-650 DEG C of insulation 120 minutes, then quenching in water, obtains ZnO-Li after cooling
2o-Bi
2o
3glass powder, ground 200 mesh sieves, for subsequent use.
6. a kind of High-frequency grain boundary layer ceramic capacitor medium as claimed in claim 1, it is characterized in that described medium composition calculates according to weight percent is: (Sr
0.96ba
0.04) TiO
389-94%, Ba (Li
1/4nb
3/4) O
30.3-2.5%, Dy
2o
30.3-3.5%, SiO
20.1-1.5%, Al
2o
30.1-2%, SrCO
30.05-1.6%, ZnO-Li
2o-Bi
2o
3glass powder 0.2-1.8%, CuO0.06-2%.
7. a kind of High-frequency grain boundary layer ceramic capacitor medium as claimed in claim 1, it is characterized in that described medium composition calculates according to weight percent is: (Sr
0.96ba
0.04) TiO
390-94%, Ba (Li
1/4nb
3/4) O
30.3-2.0%, Dy
2o
30.3-2.8%, SiO
20.1-1.3%, Al
2o
30.1-1.6%, SrCO
30.08-1.5%, ZnO-Li
2o-Bi
2o
3glass powder 0.3-1.5%, CuO0.1-1.8%.
8. the preparation method of a kind of High-frequency grain boundary layer ceramic capacitor medium as claimed in claim 1, is characterized in that comprising the steps: to adopt conventional chemical feedstocks solid phase method to synthesize (Sr respectively
0.96ba
0.04) TiO
3, Ba (Li
1/4nb
3/4) O
3and ZnO-Li
2o-Bi
2o
3glass powder, then by above-mentioned formula batching, the material distilled water prepared or deionized water are adopted the mixing of planetary ball mill ball milling, material, the mass ratio of ball and water is 1:3:0.6 ~ 1.0, ball milling is after 4 ~ 8 hours, dry to obtain dry mash, in dry mash, add the concentration accounting for its weight 8 ~ 10% is the polyvinyl alcohol solution of 10wt%, carry out granulation, mixed rear mistake 40 mesh sieve, under 20 ~ 30Mpa pressure, carry out dry-pressing again become green sheet, first binder removal before 500 DEG C in nitrogen, then heat up with the speed of 30 ~ 50 DEG C/h after higher than 1000 DEG C, then in 1270 ~ 1290 DEG C of insulations, 3 ~ 5 hours sintering, then be cooled to 900 ~ 950 DEG C in air, be incubated process in 2 ~ 3 hours, last furnace cooling, at 780 ~ 800 DEG C, insulation carries out silver ink firing in 15 minutes again, form silver electrode, solder taul again, encapsulate, obtain boundary ceramics electrical condenser.
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| CN103524127B true CN103524127B (en) | 2015-03-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105272362B (en) * | 2015-11-10 | 2017-06-30 | 电子科技大学 | Intergranular semiconductor potsherd oxidant coating material and preparation method thereof |
| CN106587996B (en) * | 2016-11-14 | 2020-03-31 | 江苏大学 | High-frequency grain boundary layer ceramic capacitor medium |
| CN106587989B (en) * | 2016-11-15 | 2019-08-02 | 江苏大学 | A kind of high dielectric property grain boundary layer ceramic capacitor medium |
| CN106631005B (en) * | 2017-01-10 | 2020-01-14 | 北京元六鸿远电子科技股份有限公司 | Medium-temperature sintered lead-free high-voltage capacitor dielectric ceramic material and preparation method thereof |
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| US4379854A (en) * | 1981-02-06 | 1983-04-12 | Erie Technological Products, Inc. | Low temperature firing (1800°-2100° F.) of barium titanate with flux (lead titanate-bismuth titanate-zinc oxide and boron oxide) |
| JPS61250905A (en) * | 1985-04-26 | 1986-11-08 | ティーディーケイ株式会社 | Dielectric ceramic composition and manufacture thereof |
| CN102436929B (en) * | 2011-07-22 | 2014-07-16 | 中国科学院上海硅酸盐研究所 | High-dielectric low-loss imitation grain boundary layer capacitor and preparation method thereof |
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