CN1179913C - Quasi-nano BazTi9O20 microwave ceramic and making method thereof - Google Patents
Quasi-nano BazTi9O20 microwave ceramic and making method thereof Download PDFInfo
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- CN1179913C CN1179913C CNB011395168A CN01139516A CN1179913C CN 1179913 C CN1179913 C CN 1179913C CN B011395168 A CNB011395168 A CN B011395168A CN 01139516 A CN01139516 A CN 01139516A CN 1179913 C CN1179913 C CN 1179913C
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Abstract
The present invention relates to a ceramic composition with components as characteristics on the basis of oxide. Sub-nanometer Ba2Ti9O20 microwave ceramics are prepared from main components such as Ba(OH)2.8H2O and TiO2, and a small quantity of additive substances such as Al2O3, SiO2 and Bi2O3. The present invention comprises the technology steps: the main constituents are placed in a high-pressure reaction vessel, and are neutralized and dried, the additive substances are added to be formed, and the microwave dielectric ceramics with fine and uniform crystal particle without air hole and good performance are prepared. The obtained samples have good microwave performance, and the particle size of visible powder is 40 to 200 nm by transmission electron microanalysis by sampling.
Description
Technical field
The present invention relates to a kind of based on oxide compound be the ceramic composition of feature with the composition, the quasi-nano two barium nine titanium oxide (Ba that especially a kind of particle diameter is 40～200nm
2Ti
9O
20) microwave ceramics and manufacture method thereof.
Background technology
Microwave ceramics generally adopted the solid reaction process preparation in the past, through composition of raw materials weighing, ball milling, calcining, pulverizing, granulation, moulding and operations such as sintering and metallization, carried out the detection of microwave property at last.Traditional solid reaction process is because the powder particle is thicker, and various diffusion of components reactions are difficult to full and uniform, and the ceramic crystalline grain size that makes is usually in the micron number magnitude, and it is bigger that grain size differs, and also has defectives such as pore, makes microwave property be difficult to further improve.And modern microwave technology development rapidly, and particularly mobile communication technology is just developing towards higher frequency, bigger bandwidth and microminiaturized direction, and objective requirement microwave ceramics and device thereof have more excellent performance.
The CN1232801A patent application discloses a kind of high-permittivity microwave medium ceramics and preparation method thereof, its principal constituent BaO, Ln
2O
3(Ln is La or Sm), TiO
2, Ta
2O
5, minor component is (La
0.1Bi
0.9)
2Ti
2O
7The content of each composition in the principal constituent (mole %) is respectively BaO:8.34～41.66, Ln
2O
3: 4.17～20.83, TiO
2: 25.0～58.33, Ta
2O
5: 12.5～29.17, the content of minor component (weight %) is 0～35.The employing correlation method is prepared from, and this microwave-medium ceramics plays specific inductivity up to 100～210, has low-loss and less temperature coefficient of resonance frequency simultaneously.
The CN1158599A patent application provides a kind of dielectric porcelain composition and manufacture method thereof, and these stupaliths are to allow Ba (Zn
1/3, Ta
2/3) O
3System or Ba (Mg
1/3, Ta
2/3) O
3The stupalith of system contains CaTiO
3, or MgTiO
3And/or SrTiO
3, and can add SiO as the sintering subsidiary material
2And/or B
2O
3, MnO and/or ZnO.These stupaliths have big nonloaded Q and high specific inductivity and little temperature coefficient of resonance frequency.These stupaliths can both be used than low in the past firing temperature (1200～1650 ℃) and easily make.
The CN1189479A patent application discloses a kind of high frequency Mb
2O
5-ZnO-Bi
2O
3Three component system medium ceramic material and preparation method, the new compositing area (mol%) that provides is: NbO
6/233.0-44.0, ZnO21.0-32.0, BiO
1/229.0-39.0.Preparation technology of the present invention is identical with the conventional oxide ceramic process.In preparation process, as regulating electrical property, use dyad Ba, Sr, Ca partly replace Zn, its separately and and Ca and Ba or the compound replacement add-on of Sr (mol%) be: Ba0.5-6.0, Sr0.5-6.0, Ca3.0-26.0, the big add-on of compound replacement amount is 26.0, and preferable dielectric properties are arranged.
The CN1218779A patent application provides a kind of high frequency Nb
2O
5-ZnO-Bi
2O
3Three component system medium ceramic material and preparation technology, the new compositing area (mol%) that provides is: MbO
6/235.0-41.0%, ZnO20.0-25.0mol%, BiO
3/238.0-44.0.In preparation process, as sintering aid be: LiF0.01-3.0, CuO0.01-1.0, V with the add-on (wt%) of low melting component (independent or compound interpolation)
2O
50.01-1.0, H
3BO
30.01-1.0, Pb
3O
40.01-3.0.As regulating electrical property, the dyad that replaces Zn is Ba, Sr, Ca, and its independent or compound replacement add-on (mol%) is: Ba0.5-6.0, Sr0.5-6.0, Ca1.0-24.0.The invention provides sintering temperature≤900 ℃ of relevant media ceramic, the sintering range broad is about 60-80 ℃, and has preferable dielectric properties.
Summary of the invention
The object of the present invention is to provide a kind of crystal grain tiny evenly, contain the quasi-nano Ba of pore and excellent property hardly
2Ti
9O
20The prescription of microwave ceramics and with hydro-thermal manufactured quasi-nano Ba
2Ti
9O
20The method of microwave ceramics.
Quasi-nano Ba
2Ti
9O
20Microwave ceramics is by principal constituent: barium hydroxide solution (Ba (OH)
28H
2O) and titanium dioxide (TiO
2) and micro-additive: aluminium sesquioxide (Al
2O
3), silicon-dioxide (SiO
2) and bismuthous oxide bismuth trioxide (Bi
2O
3) form, each components contents (in molar ratio) is Ba (OH)
28HO and TiO
2In 1: the ratio of (3～6), Al
2O
3Be 0.1～2wt%, SiO
2Be 0.1～3wt%, Bi
2O
3Be 0.5～5wt%.
Quasi-nano Ba
2Ti
9O
20The manufacture method of microwave ceramics:
1) above-mentioned each principal constituent is placed autoclave by proportioning, be warming up to 150～200 ℃ and carry out hydro-thermal reaction, constant temperature time is 1～40h;
2) reaction product is washed and suction filtration, make neutral after drying;
3) add above-mentioned micro-additive, carry out ball milling, oven dry, granulation, moulding, and be incubated 1～5h down, promptly make said quasi-nano BazTi 9 O 20 microwave ceramic at 1250～1300 ℃.
The present invention adopts the Ba of Hydrothermal Preparation quasi-nano
2Ti
9O
20Micro crystalline powder, and add minor component Al
2O
3, SiO
2And Bi
2O
3, through 1250～1300 ℃ of sintering temperatures insulation 1～5 hour, make crystal grain tiny evenly, contain the microwave-medium ceramics of pore and excellent property hardly.The transmission electron microscopy analysis is carried out in sampling, and visible powder granule size is 40～200nm.The sample of gained has obviously superior microwave property.Referring to following specific embodiment.
Embodiment
According to the principal constituent of above-mentioned quasi-nano BazTi 9 O 20 microwave ceramic and the proportioning and the manufacture method of micro-additive, table 1 provides the data of each embodiment, and table 2 provides the performance of each embodiment.
The Ba of table 1 Hydrothermal Preparation quasi-nano
2Ti
9O
20The data of micro crystalline powder
| The embodiment sample number into spectrum | Ba(OH) 2·8H 2O/TiO 2(mol ratio) | Al 2O 3 SiO 2 Bi 2O 3(wt％)(wt％)(wt％) | Constant temperature time (h) | Granular size (nm) |
| 01 | 1/3 | 0.1 3.0 0.5 | 1 5 10 20 40 | 40 90 150 200 200 |
| 02 | 1/3 | 0.5 2.0 3.0 | 1 5 10 20 40 | 50 80 140 190 200 |
| 03 | 1/3 | 1.0 1.0 5.0 | 1 5 10 20 40 | 40 80 130 180 200 |
| 04 | 1/3 | 2.0 0.1 1.0 | 1 5 10 20 40 | 50 90 150 190 200 |
| 05 | 1/4 | 0.1 3.0 0.5 | 1 5 10 20 40 | 40 80 140 190 200 |
| 06 | 1/4 | 0.5 2.0 3.0 | 1 5 10 20 40 | 50 90 140 200 200 |
| 07 | 1/4 | 1.0 1.0 5.0 | 1 5 10 20 40 | 50 80 140 180 200 |
| 08 | 1/4 | 2.0 0.1 1.0 | 1 5 10 20 40 | 40 90 150 200 200 |
| 09 | 1/4.5 | 0.1 3.0 0.5 | 1 5 10 20 40 | 50 80 150 190 200 |
| 10 | 1/4.5 | 0.5 2.0 3.0 | 1 5 10 20 40 | 50 100 140 190 200 |
| 11 | 1/4.5 | 1.0 1.0 5.0 | 1 5 10 20 40 | 40 90 140 180 200 |
| 12 | 1/4.5 | 2.0 0.1 1.0 | 1 5 10 20 40 | 40 80 130 190 200 |
| 13 | 1/5 | 0.1 3.0 0.5 | 1 5 10 20 40 | 50 90 140 190 200 |
| 14 | 1/5 | 0.5 2.0 3.0 | 1 5 10 20 40 | 40 90 140 190 200 |
| 15 | 1/5 | 1.0 1.0 5.0 | 1 5 10 20 40 | 40 100 140 190 200 |
| 16 | 1/5 | 2.0 0.1 1.0 | 1 5 10 20 40 | 50 80 140 200 200 |
| 17 | 1/6 | 0.1 3.0 0.5 | 1 5 10 20 40 | 50 100 140 200 200 |
| 18 | 1/6 | 0.5 2.0 3.0 | 1 5 10 20 40 | 40 90 150 190 200 |
| 19 | 1/6 | 1.0 1.0 5.0 | 1 5 10 20 40 | 40 90 140 180 200 |
| 20 | 1/6 | 2.0 0.1 1.0 | 1 5 10 20 40 | 50 100 140 190 200 |
Table 2 adopts Hydrothermal Preparation quasi-nano Ba
2Ti
9O
20Powder makes the microwave ceramics performance
| The embodiment sample number into spectrum | Firing temperature (℃) | Soaking time (h) | DIELECTRIC CONSTANT | Q·f | τ f (ppm/℃) |
| 01 | 1250 1275 1300 | 5 2.5 1 | 20 25 28 | 43,000 42,000 40,000 | +3 +5 -2 |
| 02 | 1250 1275 1300 | 5 2.5 1 | 24 27 32 | 32,000 40,000 36,000 | +4 +6 +8 |
| 03 | 1250 1275 1300 | 5 2.5 1 | 22 29 31 | 40,000 38,000 36,000 | +3 +4 -1 |
| 04 | 1250 1275 1300 | 5 2.5 1 | 23 26 29 | 40,000 38,000 36,000 | -2 -4 -7 |
| 05 | 1250 1275 1300 | 5 2.5 1 | 27 32 38 | 45,000 43,000 41,000 | +4 +6 -1 |
| 06 | 1250 1275 1300 | 5 2.5 1 | 28 34 39 | 49,000 45,000 39,000 | +4 +6 +8 |
| 07 | 1250 1275 1300 | 5 2.5 1 | 30 36 40 | 48,000 43,000 35,000 | +8 +6 +3 |
| 08 | 1250 1275 1300 | 5 2.5 1 | 30 36 40 | 48,000 43,000 35,000 | +8 +6 +3 |
| 09 | 1250 1275 1300 | 5 2.5 1 | 32 38 45 | 49,000 45,000 40,000 | +9 +7 +5 |
| 10 | 1250 1275 1300 | 5 2.5 1 | 34 39 44 | 48,000 46,000 41,000 | +9 +8 +4 |
| 11 | 1250 1275 1300 | 5 2.5 1 | 33 38 43 | 49,000 46,000 42,000 | +9 +7 +4 |
| 12 | 1250 1275 1300 | 5 2.5 1 | 35 40 44 | 48,000 45,000 40,000 | +8 +7 +2 |
| 13 | 1250 1275 1300 | 5 2.5 1 | 32 38 41 | 47,000 44,000 42,000 | +5 +4 +1 |
| 14 | 1250 1275 1300 | 5 2.5 1 | 33 37 40 | 48,000 45,000 41,000 | +6 +4 +2 |
| 15 | 1250 1275 1300 | 5 2.5 1 | 30 34 38 | 49,000 46,000 42,000 | +5 +2 +1 |
| 16 | 1250 1275 1300 | 5 2.5 1 | 24 27 31 | 45,000 43,000 40,000 | +4 +1 -2 |
| 17 | 1250 1275 1300 | 5 2.5 1 | 22 25 19 | 46,000 42,000 39,000 | +3 -3 -5 |
| 18 | 1250 1275 1300 | 5 2.5 1 | 20 24 21 | 44,000 41,000 38,000 | +1 -3 -6 |
| 19 | 1250 1275 1300 | 5 2.5 1 | 23 21 20 | 43,000 41,000 37,000 | +3 -5 -2 |
| 20 | 1250 1275 1300 | 5 2.5 1 | 24 22 18 | 43,000 40,000 41,000 | +1 -5 -8 |
Claims (2)
1. quasi-nano Ba
2Ti
9O
20Microwave ceramics is characterized in that by principal constituent: Ba (OH)
28H
2O and TiO
2And micro-additive: Al
2O
3, SiO
2And Bi
2O
3Form, each component content in molar ratio is Ba (OH)
28HO/TiO
2For: 1: (3～6), Al
2O
3Be 0.1～2wt%, SiO
2Be 0.1～3wt%, Bi
2O
3Be 0.5～5wt%.
2. the manufacture method of microwave ceramics as claimed in claim 1 is characterized in that
1) each principal constituent is placed autoclave by proportioning, be warming up to 150～200 ℃ and carry out hydro-thermal reaction, constant temperature time is 1～40h;
2) product is washed and suction filtration, make neutral after drying;
3) add micro-additive, carry out ball milling, oven dry, granulation, moulding, and be incubated 1～5h down, promptly make said quasi-nano BazTi 9 O 20 microwave ceramic at 1250～1300 ℃.
4) said principal constituent is: Ba (OH)
28H
2O and TiO
2, its content in molar ratio is Ba (OH)
28HO/TiO
2Be 1: (3～6);
5) said micro-additive is Al
2O
30.1～2wt%, SiO
20.1～3wt%, Bi
2O
30.5～5wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011395168A CN1179913C (en) | 2001-11-20 | 2001-11-20 | Quasi-nano BazTi9O20 microwave ceramic and making method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011395168A CN1179913C (en) | 2001-11-20 | 2001-11-20 | Quasi-nano BazTi9O20 microwave ceramic and making method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1420102A CN1420102A (en) | 2003-05-28 |
| CN1179913C true CN1179913C (en) | 2004-12-15 |
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|---|---|---|---|
| CNB011395168A Expired - Fee Related CN1179913C (en) | 2001-11-20 | 2001-11-20 | Quasi-nano BazTi9O20 microwave ceramic and making method thereof |
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| CN102531572A (en) * | 2010-12-13 | 2012-07-04 | 王强 | Temperature compensation high-frequency microwave capacitor medium material |
| CN102531573A (en) * | 2010-12-13 | 2012-07-04 | 王强 | Doped and modified temperature compensation high-frequency microwave capacitor dielectric material |
| CN103708541A (en) * | 2013-12-26 | 2014-04-09 | 天津大学 | Method for preparing barium nonatitanate by liquid-phase process |
| CN108484160A (en) * | 2018-06-25 | 2018-09-04 | 苏州博恩希普新材料科技有限公司 | Nine barium phthalate base microwave dielectric ceramic materials of one kind and preparation method |
| CN110655378B (en) * | 2018-06-29 | 2022-02-15 | 昆山微电子技术研究院 | Preparation method of composite material for flexible circuit board |
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