CN101811864A - Microwave medium ceramic material of near-zero resonance frequency temperature coefficient and preparation method thereof - Google Patents
Microwave medium ceramic material of near-zero resonance frequency temperature coefficient and preparation method thereof Download PDFInfo
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- CN101811864A CN101811864A CN 201010151737 CN201010151737A CN101811864A CN 101811864 A CN101811864 A CN 101811864A CN 201010151737 CN201010151737 CN 201010151737 CN 201010151737 A CN201010151737 A CN 201010151737A CN 101811864 A CN101811864 A CN 101811864A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 238000000748 compression moulding Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000003595 mist Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000011236 particulate material Substances 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000001238 wet grinding Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 4
- 239000008187 granular material Substances 0.000 abstract 2
- 230000032683 aging Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 238000004891 communication Methods 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007274 generation of a signal involved in cell-cell signaling Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005316 response function Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a microwave medium ceramic material of a near-zero resonance frequency temperature coefficient and a preparation method thereof. The microwave medium ceramic material consists of 40 to 48 percent of MgO, 2 to 10 percent of CaO and 50 percent of TiO2 in percentage by weight; and the dielectric constant is 15 to 40, the quality factor is 10,000 to 120,000GHz, and the resonance frequency temperature coefficient is -15 to 15ppm/DEG C. The preparation method comprises the following steps: mixing, grinding and drying the MgO, the CaO and the TiO2; then burning the mixture for 2 to 4 hours, secondarily mixing and grinding the mixture to form slurry, adding PVA into the slurry, and ageing, spraying and granulating the mixture to form powdery granules; and pressing the powdery granules to form products with various shapes, and sintering the products 2 to 4 hours and then cooling the products. The microwave medium ceramic material has good transmission signal response speed, environment working temperature stability, signal selectivity, high temperature resistant, chemical corrosion resistance, moisture resistance and mechanical bearing capacity.
Description
Technical field
The invention belongs to function electronic information material and devices field, be specifically related to microwave dielectric ceramic materials of the good near-zero resonance frequency temperature coefficient of a kind of novel service temperature stability and preparation method thereof.
Background technology
Fast development along with the communications electronics technology, the system signal generation of playing that is fit to various frequency range communications electronics Circuits System needs is also paid close attention to widely with the research and development of the critical material of response function core devices such as (resonance and filtering, conduction and isolation).Particularly in the modern communications microwave frequency under the background that the millimeter wave sub-millimeter wave direction of microwave high-frequency section develops, develop that all kinds of transmission signal responses are fast, frequency selectivity is strong and the operating ambient temperature good stability be adapted at the middle low-k multiplayer microwave dielectric resonator, vibrator, wave filter, microwave antenna, microwave wire and the microwave base plate material that use in WLAN base station, satellite communications and the radar system become a current big gordian technique that influences the micro-wave communication technical development.At present, the microwave dielectric material of having sold on the market mainly is the high dielectric constant pottery and composite perofskite pottery that is used for device miniaturization, as, tungsten bronze structure BaO-Ln
2O
3-TiO
2System's pottery (Ln is a rare earth element) is the compound titanium ore stupalith of calcium with barium system with calcium.And at present few for specific inductivity microwave dielectric ceramic species of near-zero resonance frequency temperature coefficient between 15～40, mainly be the MgTiO of metatitanic acid magnesium salts
3-TiO
2Composite ceramics and some perovskite ceramics.
Summary of the invention
The object of the invention is the needs at the communications electronics Circuits System, and a kind of novel near-zero resonance frequency temperature coefficient microwave dielectric ceramic materials is provided, and the preparation method of this microwave dielectric ceramic materials is provided simultaneously.
The chemical ingredients of microwave dielectric ceramic materials of the present invention is by MgO, CaO and TiO
2Three kinds of oxide compounds are formed, and wherein the mass percent of MgO is that the mass percent of 40～48wt%, CaO is 2～10wt%, TiO
2Mass percent be 50wt%.This microwave dielectric ceramic materials specific inductivity is 15～40, quality factor (Q * f value) is 10,000～120, and 000GHz, temperature coefficient of resonance frequency are-15～15ppm/ ℃.
The method for preparing this microwave dielectric ceramic materials may further comprise the steps:
Step (1) raw material is chosen: choose purity greater than 99% MgO, CaO and TiO
2As raw material;
Step (2) batching and batch mixing: raw material is pressed mass ratio MgO: CaO: TiO
2=40～48: 2～10: mix after 50 weighings, wet grinding is inserted in the drying baker after 12～24 hours and is dried in ball mill, and bake out temperature is 80 ℃～120 ℃.
Step (3) calcining and granulation: the mixture after will grinding was calcined in resistance heading furnace 2～4 hours, calcining temperature is 1000 ℃～1300 ℃, insert 12～24 hours form slurry of secondary mixed grinding in the ball mill then, in slurry, add organic binder bond polyvinyl alcohol (PVA), the organic binder bond that adds is 4～8% of a stock quality, passes through old, mist projection granulating powdered particulate material then.
Step (4) compression moulding: the powder particle material is inserted in each grinding tool in the powder pressure forming machine, under 98～100MPa pressure, be pressed into the different shape goods.
Step (5) sinters porcelain into: the compression moulding goods are 1300 ℃～1500 ℃ sintering temperatures 2～4 hours, then with the speed temperature control cooling of 2 ℃～5 ℃ of per minutes, close the temperature regulating device furnace cooling after arriving 1000 ℃～1200 ℃.
Step (6) later stage mechanical workout and device assembling.
The present invention is at 2MgO-TiO
2Introduce the CaO-A position in the prescription and change modification formation MgO-CaO-TiO
2The system pottery.This kind pottery significantly overcomes original 2MgO-TiO
2The defective of ambient operating temperature poor stability of pottery, its temperature coefficient of resonance frequency is in-15ppm/ ℃～15ppm/ ℃ scope.Under Working environment, its frequency stabilization is good, is not easy to drift about.Microwave dielectric ceramic materials of the present invention is abundant and satisfied the demand of current communications electronics Circuits System to the strong middle low-dielectric constant dielectric medium material of operating ambient temperature good stability and frequency selectivity.This media ceramic specific inductivity is between 15～40, quality factor is 10,000～110, in the 000GHz scope, have good transmission signal response speed, ambient operating temperature stability, signal-selectivity and the good wet and favorable mechanical supporting capacity of high temperature resistance, resist chemical, moisture resistance, can be used as multiplayer microwave resonator, oscillator filter, microwave antenna, microwave wire and microwave base plate and electronic circuit board material and use.
Embodiment
The chemical ingredients of the microwave dielectric ceramic materials of near-zero resonance frequency temperature coefficient is by MgO, CaO and TiO
2Three kinds of oxide compounds are formed, and wherein the mass percent of MgO is that the mass percent of 40～48wt%, CaO is 2～10wt%, TiO
2Mass percent be 50wt%.This microwave dielectric ceramic materials specific inductivity is 15～40, quality factor (Q * f value) is 10,000～120, and 000GHz, temperature coefficient of resonance frequency are-15～15ppm/ ℃.
Embodiment 1.
Step (1) raw material is chosen: choose purity greater than 99% MgO, CaO and TiO
2As raw material;
Step (2) batching and batch mixing: press mass ratio MgO: CaO: TiO
2=48: mix after the weighing in 2: 50, wet grinding is inserted in the drying baker after 12 hours and is dried in ball mill, and bake out temperature is 120 ℃.
Step (3) calcining and granulation: the mixture after will grinding was calcined in resistance heading furnace 2 hours, calcining temperature is 1300 ℃, insert 12 hours form slurry of secondary mixed grinding in the ball mill then, in slurry, add organic binder bond PVA, the organic binder bond that adds is 8% of a stock quality, passes through old, mist projection granulating powdered particulate material then.
Step (4) compression moulding: the powder particle material is inserted in each grinding tool in the powder pressure forming machine, under 98MPa pressure, be pressed into the different shape goods.
Step (5) sinters porcelain into: the compression moulding goods are 1500 ℃ of sintering temperatures 2 hours, then with the speed temperature control cooling of 5 ℃ of per minutes, close the temperature regulating device furnace cooling after arriving 1000 ℃.
Step (6) later stage mechanical workout and device assembling.
The chemical ingredients of the microwave dielectric ceramic materials of preparation is by MgO, CaO and TiO
2Three kinds of oxide compounds are formed, and wherein the mass percent of MgO is that the mass percent of 48wt%, CaO is 2wt%, TiO
2Mass percent be 50wt%.This microwave dielectric ceramic materials specific inductivity is 15, quality factor (Q * f value) is 120,000GHz, temperature coefficient of resonance frequency be-and 15ppm/ ℃.
Embodiment 2:
Step (1) raw material is chosen: choose purity greater than 99% MgO, CaO and TiO
2As raw material;
Step (2) batching and batch mixing: press mass ratio MgO: CaO: TiO
2=46: mix after the weighing in 4: 50, wet grinding is inserted in the drying baker after 15 hours and is dried in ball mill, and bake out temperature is 120 ℃.
Step (3) calcining and granulation: the mixture after will grinding was calcined in resistance heading furnace 2.5 hours, calcining temperature is 1250 ℃, insert 12 hours form slurry of secondary mixed grinding in the ball mill then, in slurry, add organic binder bond PVA, the organic binder bond that adds is 5% of a stock quality, passes through old, mist projection granulating powdered particulate material then.
Step (4) compression moulding: the powder particle material is inserted in each grinding tool in the powder pressure forming machine, under 99MPa pressure, be pressed into the different shape goods.
Step (5) sinters porcelain into: the compression moulding goods are 1400 ℃ of sintering temperatures 3 hours, then with the speed temperature control cooling of 4 ℃ of per minutes, close the temperature regulating device furnace cooling after arriving 1200 ℃.
Step (6) later stage mechanical workout and device assembling.
The chemical ingredients of the microwave dielectric ceramic materials of preparation is by MgO, CaO and TiO
2Three kinds of oxide compounds are formed, and wherein the mass percent of MgO is that the mass percent of 46wt%, CaO is 4wt%, TiO
2Mass percent be 50wt%.This microwave dielectric ceramic materials specific inductivity is 23, quality factor (Q * f value) is 58,200GHz, temperature coefficient of resonance frequency be-and 7ppm/ ℃.
Embodiment 3:
Step (1) raw material is chosen: choose purity greater than 99% MgO, CaO and TiO
2As raw material;
Step (2) batching and batch mixing: press mass ratio MgO: CaO: TiO
2=43: mix after the weighing in 7: 50, wet grinding is inserted in the drying baker after 24 hours and is dried in ball mill, and bake out temperature is 80 ℃.
Step (3) calcining and granulation: the mixture after will grinding was calcined in resistance heading furnace 3 hours, calcining temperature is 1200 ℃, insert 12 hours form slurry of secondary mixed grinding in the ball mill then, in slurry, add organic binder bond PVA, the organic binder bond that adds is 6% of a stock quality, passes through old, mist projection granulating powdered particulate material then.
Step (4) compression moulding: the powder particle material is inserted in each grinding tool in the powder pressure forming machine, under 98MPa pressure, be pressed into the different shape goods.
Step (5) sinters porcelain into: the compression moulding goods are 1350 ℃ of sintering temperatures 4 hours, then with the speed temperature control cooling of 3 ℃ of per minutes, close the temperature regulating device furnace cooling after arriving 1150 ℃.
Step (6) later stage mechanical workout and device assembling.
The chemical ingredients of the microwave dielectric ceramic materials of preparation is by MgO, CaO and TiO
2Three kinds of oxide compounds are formed, and wherein the mass percent of MgO is that the mass percent of 43wt%, CaO is 7wt%, TiO
2Mass percent be 50wt%.This microwave dielectric ceramic materials specific inductivity is 30, quality factor (Q * f value) is 20,400GHz, temperature coefficient of resonance frequency be+and 10ppm/ ℃.
Embodiment 4:
Step (1) raw material is chosen: choose purity greater than 99% MgO, CaO and TiO
2As raw material;
Step (2) batching and batch mixing: press mass ratio MgO: CaO: TiO
2=40: mix after the weighing in 10: 50, wet grinding is inserted in the drying baker after 18 hours and is dried in ball mill, and bake out temperature is 100 ℃.
Step (3) calcining and granulation: the mixture after will grinding was calcined in resistance heading furnace 4 hours, calcining temperature is 1000 ℃, insert 12 hours form slurry of secondary mixed grinding in the ball mill then, in slurry, add organic binder bond PVA, the organic binder bond that adds is 4% of a stock quality, passes through old, mist projection granulating powdered particulate material then.
Step (4) compression moulding: the powder particle material is inserted in each grinding tool in the powder pressure forming machine, under 100MPa pressure, be pressed into the different shape goods.
Step (5) sinters porcelain into: the compression moulding goods are 1300 ℃ of sintering temperatures 4 hours, then with the speed temperature control cooling of 2 ℃ of per minutes, close the temperature regulating device furnace cooling after arriving 1100 ℃.
Step (6) later stage mechanical workout and device assembling.
The chemical ingredients of the microwave dielectric ceramic materials of preparation is by MgO, CaO and TiO
2Three kinds of oxide compounds are formed, and wherein the mass percent of MgO is that the mass percent of 40wt%, CaO is 10wt%, TiO
2Mass percent be 50wt%.This microwave dielectric ceramic materials specific inductivity is 40, quality factor (Q * f value) is 10,000GHz, temperature coefficient of resonance frequency be+and 15ppm/ ℃.
Above-mentioned laboratory embodiment just is used for explaining the present invention, rather than limits the invention.In the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (2)
1. the microwave dielectric ceramic materials of near-zero resonance frequency temperature coefficient is characterized in that this microwave dielectric ceramic materials is by MgO, CaO and TiO
2Three kinds of oxide compounds are formed, and wherein the mass percent of MgO is that the mass percent of 40～48wt%, CaO is 2～10wt%, TiO
2Mass percent be 50wt%; This microwave dielectric ceramic materials specific inductivity is 15～40, quality factor is 10,000～120, and 000GHz, temperature coefficient of resonance frequency are-15～15ppm/ ℃.
2. prepare the method for the microwave dielectric ceramic materials of near-zero resonance frequency temperature coefficient, it is characterized in that the concrete steps of this method are:
Step (1) raw material is chosen: choose purity greater than 99% MgO, CaO and TiO
2As raw material;
Step (2) batching and batch mixing: raw material is pressed mass ratio MgO: CaO: TiO
2=40～48: 2～10: mix after 50 weighings, wet grinding is inserted in the drying baker after 12～24 hours and is dried in ball mill, and bake out temperature is 80 ℃～120 ℃;
Step (3) calcining and granulation: the mixture after will grinding was calcined in resistance heading furnace 2～4 hours, calcining temperature is 1000 ℃～1300 ℃, insert 12～24 hours form slurry of secondary mixed grinding in the ball mill then, in slurry, add the organic binder bond polyvinyl alcohol, the amount of the polyvinyl alcohol that adds is 4～8% of a stock quality, passes through old, mist projection granulating powdered particulate material then;
Step (4) compression moulding: the powder particle material is inserted in each grinding tool in the powder pressure forming machine, under 98～100MPa pressure, be pressed into the different shape goods;
Step (5) sinters porcelain into: the compression moulding goods are 1300 ℃～1500 ℃ sintering temperatures 2～4 hours, then with the speed temperature control cooling of 2 ℃～5 ℃ of per minutes, close the temperature regulating device furnace cooling after arriving 1000 ℃～1200 ℃;
Step (6) later stage mechanical workout and device assembling.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010151737 CN101811864A (en) | 2010-04-20 | 2010-04-20 | Microwave medium ceramic material of near-zero resonance frequency temperature coefficient and preparation method thereof |
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|---|---|---|---|
| CN 201010151737 CN101811864A (en) | 2010-04-20 | 2010-04-20 | Microwave medium ceramic material of near-zero resonance frequency temperature coefficient and preparation method thereof |
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| CN101811864A true CN101811864A (en) | 2010-08-25 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102318135A (en) * | 2010-11-01 | 2012-01-11 | 华为技术有限公司 | Production Method of Microwave Dielectric Resonator and Microwave Dielectric Duplexer |
| CN103172364A (en) * | 2011-12-22 | 2013-06-26 | 深圳市大富科技股份有限公司 | Preparation method of microwave dielectric ceramic material |
| CN109279892A (en) * | 2018-11-21 | 2019-01-29 | 湖北天瓷电子材料有限公司 | A method for preparing microwave ceramic pre-fired powder by using co-precipitation method |
| CN109467432A (en) * | 2018-12-14 | 2019-03-15 | 电子科技大学 | A kind of Mg-Ti-Ta based microwave dielectric ceramic material and preparation method thereof |
| CN110862256A (en) * | 2019-11-13 | 2020-03-06 | 深圳顺络电子股份有限公司 | Preparation method of microwave dielectric sintered powder material, microwave dielectric ceramic and application thereof |
| CN112397861A (en) * | 2020-11-03 | 2021-02-23 | 南京新智电子材料科技有限公司 | Medium ring and medium pipe for mobile communication isolator and circulator |
| CN115490512A (en) * | 2022-09-19 | 2022-12-20 | 大富科技(安徽)股份有限公司 | 5G microwave dielectric ceramic material, preparation method thereof and microwave dielectric ceramic device |
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| US5449652A (en) * | 1993-06-04 | 1995-09-12 | Battelle Memorial Institute | Ceramic compositions for BZN dielectric resonators |
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| 《中国博士学位论文全文数据库工程科技Ⅰ辑》 20070815 宋开新 "低介电常数微波介质陶瓷" , 第2期 2 * |
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Cited By (13)
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|---|---|---|---|---|
| WO2012058916A1 (en) * | 2010-11-01 | 2012-05-10 | 华为技术有限公司 | Microwave dielectric resonator, preparation method thereof, and microwave dielectric duplexer |
| CN102318135B (en) * | 2010-11-01 | 2014-04-30 | 华为技术有限公司 | Microwave dielectric resonator, production method thereof, and microwave dielectric duplexer |
| CN102318135A (en) * | 2010-11-01 | 2012-01-11 | 华为技术有限公司 | Production Method of Microwave Dielectric Resonator and Microwave Dielectric Duplexer |
| CN103172364A (en) * | 2011-12-22 | 2013-06-26 | 深圳市大富科技股份有限公司 | Preparation method of microwave dielectric ceramic material |
| CN109279892A (en) * | 2018-11-21 | 2019-01-29 | 湖北天瓷电子材料有限公司 | A method for preparing microwave ceramic pre-fired powder by using co-precipitation method |
| CN109467432B (en) * | 2018-12-14 | 2021-03-30 | 电子科技大学 | Mg-Ti-Ta-based microwave dielectric ceramic material and preparation method thereof |
| CN109467432A (en) * | 2018-12-14 | 2019-03-15 | 电子科技大学 | A kind of Mg-Ti-Ta based microwave dielectric ceramic material and preparation method thereof |
| CN110862256A (en) * | 2019-11-13 | 2020-03-06 | 深圳顺络电子股份有限公司 | Preparation method of microwave dielectric sintered powder material, microwave dielectric ceramic and application thereof |
| CN110862256B (en) * | 2019-11-13 | 2021-12-03 | 深圳顺络电子股份有限公司 | Preparation method of microwave dielectric sintered powder material, microwave dielectric ceramic and application thereof |
| CN112397861A (en) * | 2020-11-03 | 2021-02-23 | 南京新智电子材料科技有限公司 | Medium ring and medium pipe for mobile communication isolator and circulator |
| CN112397861B (en) * | 2020-11-03 | 2022-05-20 | 南京新智电子材料科技有限公司 | Medium ring and medium pipe for mobile communication isolator or circulator |
| CN115490512A (en) * | 2022-09-19 | 2022-12-20 | 大富科技(安徽)股份有限公司 | 5G microwave dielectric ceramic material, preparation method thereof and microwave dielectric ceramic device |
| CN115490512B (en) * | 2022-09-19 | 2023-10-20 | 大富科技(安徽)股份有限公司 | 5G microwave dielectric ceramic material, preparation method thereof and microwave dielectric ceramic device |
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Application publication date: 20100825 |