CN103880288A - Strontium barium niobate glass ceramic material with high dielectric constant and high breakdown field strength and preparation method thereof - Google Patents
Strontium barium niobate glass ceramic material with high dielectric constant and high breakdown field strength and preparation method thereof Download PDFInfo
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- CN103880288A CN103880288A CN201410040185.9A CN201410040185A CN103880288A CN 103880288 A CN103880288 A CN 103880288A CN 201410040185 A CN201410040185 A CN 201410040185A CN 103880288 A CN103880288 A CN 103880288A
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- barium niobate
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- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000006112 glass ceramic composition Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000015556 catabolic process Effects 0.000 title abstract description 4
- 238000002425 crystallisation Methods 0.000 claims abstract description 44
- 230000008025 crystallization Effects 0.000 claims abstract description 44
- 238000002844 melting Methods 0.000 claims abstract description 34
- 230000008018 melting Effects 0.000 claims abstract description 34
- 238000000137 annealing Methods 0.000 claims abstract description 29
- 238000000465 moulding Methods 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims description 54
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 24
- 238000004455 differential thermal analysis Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 2
- 239000002241 glass-ceramic Substances 0.000 abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 238000002441 X-ray diffraction Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- 239000005347 annealed glass Substances 0.000 abstract 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 2
- 229910001632 barium fluoride Inorganic materials 0.000 abstract 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract 1
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 12
- 238000004146 energy storage Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 235000006040 Prunus persica var persica Nutrition 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 244000144730 Amygdalus persica Species 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000002003 electrode paste Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 240000005809 Prunus persica Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
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Abstract
The invention discloses a strontium barium niobate glass ceramic material with high dielectric constant and high breakdown field strength and a preparation method thereof. The preparation method comprises the following steps: uniformly mixing SrCO3, BaCO3, Nb2O5, CaCO3, SiO2, H3BO3 and BaF2, uniformly melting at 1300-1400 DEG C, molding and rapidly annealing to obtain annealed glass; crystalizing the annealed glass at the crystallization temperature and then cooling in a furnace to obtain the strontium barium niobate glass ceramic material. By adopting a melting method to prepare the strontium barium niobate glass ceramic material, the method is simple and convenient, and various molding methods are available. The strontium barium niobate glass ceramic material is treated at first and then is subjected to XRD (X-Ray Diffraction), SEM and EDS tests, and the test results prove that the strontium barium niobate glass ceramic material prepared by the method disclosed by the invention is ferroelectric glass ceramic with high dielectric constant, high breakdown field strength and low dielectric loss.
Description
Technical field
The present invention relates to a kind of glass ceramic material and preparation method thereof, particularly strontium barium niobate glass ceramic material of the high breaking down field strength of a kind of high-k and preparation method thereof.
Background technology
In recent years, along with the develop rapidly of information technology and electronic science and technology, people are urgent to can effectively reducing the dielectric materials demand with high energy storage density of high voltage capacitor volume, electronics is proposed to higher service requirements, for example lightness and miniaturization, high energy storage material also just arises at the historic moment.The functional materials with ferroelectric properties that ferroelectric glass-ceramic is made up of ferroelectric phase and the glassy phase of high-k, it has concentrated glass and ceramic advantage, internal crystallization structure is much thinner than the crystal in many stupaliths, and more all with fine and close, almost there is no pore, dielectric loss is very little, therefore utilize the standby glass-ceramic of devitrified glass legal system to possess the double dominant of the high disruptive strength of glass state material and the high-k of dielectric ceramic system, become the focus of high energy-accumulating medium investigation of materials.
SBN glass-ceramic is used as high energy storage material owing to possessing high breaking down field strength.Glass basis is mostly SiO at present
2, it makes melt temperature up to 1500 ℃, H
3bO
3add and can make melt temperature significantly reduce.CaO reduces the stickiness of glass in the time of high temperature, impels thawing and the clarification of glass, and the crystallization tendency of glass is increased.Therefore, select CaO-SiO
2-B
2o
3(CBS) system is as glass basis.Glass add the porosity that has reduced material, increased the breaking down field strength of material, but also reduced crystallization tendency, relatively low crystallization tendency can limit the application as energy storage material.Therefore,, in order to improve the crystallization tendency of glass-ceramic, it is necessary introducing the degree of crystallinity that effective nucleator goes to improve SBN glass-ceramic.
Summary of the invention
The object of the present invention is to provide strontium barium niobate glass ceramic material of the high breaking down field strength of a kind of high-k and preparation method thereof, the method experimental implementation is simple, raw material height homogeneous reaction, and the strontium barium niobate glass ceramic material making has that breaking down field strength is high, specific inductivity is high, and strontium barium niobate glass ceramic material porosity is little.
For achieving the above object, strontium barium niobate glass ceramic material of the present invention, comprises that mol ratio is SrO, BaO, the Nb of 12:12:24:2x:2x:3x:3
2o
5, CaO, SiO
2, B
2o
3and BaF
2, and x=5～8.
The SrCO that the strontium barium niobate glass ceramic material of the high breaking down field strength of a kind of high-k is is 12:12:24:2x:2x:6x:3 by mol ratio
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2make through melting, moulding, annealing and crystallization processing.
A preparation method for the strontium barium niobate glass ceramic material of the high breaking down field strength of high-k, comprises the steps:
1) by SrCO
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2according to 12SrO-12BaO-24Nb
2o
3-2xCaO-2xSiO
2-3xB
2o
3-3BaF
2mixed in molar ratio is even, obtains mixture; Wherein, x=5～8;
2) crucible is heated to 1100 ℃ with stove, starts to add mixture, then continue to be heated to 1300-1400 ℃, at 1300-1400 ℃, insulation makes mixture melting even, obtains mixed melting material; By the moulding on mould of mixed melting material, then put into stove and anneal at 600-800 ℃, glass after being annealed;
3) after annealing, glass is incubated and carries out crystallization processing under its crystallization temperature, obtains strontium barium niobate glass ceramic material.
X=5,6,7 or 8 in described step 1).
Crystallization temperature in described step 3) is determined glass after annealing through the test of DTA differential thermal analysis.
In the time of x=5, after annealing, the crystallization temperature of glass is 1035 ℃; In the time of x=6, after annealing, the crystallization temperature of glass is 973 ℃; In the time of x=7, after annealing, the crystallization temperature of glass is 935 ℃; In the time of x=8, after annealing, the crystallization temperature of glass is 875 ℃.
In described step 3), the crystallization treatment time is 3-6h.
Described step 2) in annealing time be 4-7h.
Compared with prior art, beneficial effect of the present invention is:
Preparation method's experimental implementation of the present invention is simple, and forming method is many; It is minimum that the strontium barium niobate glass ceramic material making has void content, and through evidence, the inner peach blossom shape tridymite crystal evenly generating of strontium barium niobate glass ceramic material that the present invention makes makes breakdown strength of material high; Meanwhile, the present invention also rationally controls the ratio of ferroelectric Strontium Barium Niobate Crystal and glass content, the ferroelectric glass-ceramic of the generation high breaking down field strength of high-k and low node loss.
In addition, owing to having added BaF in preparation process
2as nucleator, BaF
2can impel glass nucleation, the microcrystal of fluorochemical is exactly the nucleation centre of glass; Meanwhile, BaF
2nucleus formation temperature, lower than crystal growth temperature, therefore, through BaF
2the glass crystal grain of coring, crystallization is tiny, and promotes separating out of Strontium Barium Niobate Crystal.And the present invention selects CaO-SiO
2-B
2o
3as glass basis, B
2o
3by H
3bO
3add introduction, be mostly SiO with current glass basis
2melt temperature (up to 1500 ℃) compare H
3bO
3can make happy and harmonious temperature significantly reduce, CaO is network modifying oxide, and Main Function is to weaken network structure, be conducive to glass founds and sintering at lower temperature, in the time of high temperature, reduce the stickiness of glass, impel thawing and the clarification of glass, the crystallization tendency of glass is increased.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the strontium barium niobate glass ceramic material prepared of the embodiment of the present invention 3;
Fig. 2 is the SEM figure of the strontium barium niobate glass ceramic material prepared of the embodiment of the present invention 3;
Fig. 3 is the EDS figure of peach blossom shape in the strontium barium niobate glass ceramic material prepared of the embodiment of the present invention 3;
Fig. 4 is the EDS figure of peach blossom shape periphery in the strontium barium niobate glass ceramic material prepared of the embodiment of the present invention 3.
Embodiment
Embodiment 1:
In the present embodiment, strontium barium niobate glass ceramic material comprises that mol ratio is SrO, BaO, the Nb of 12:12:24:10:10:15:3
2o
5, CaO, SiO
2, B
2o
3and BaF
2.
The SrCO that the present embodiment strontium barium niobate glass ceramic material is is 12:12:24:10:10:30:3 by mol ratio
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2make through melting, moulding, annealing and crystallization processing.
The preparation method of the present embodiment strontium barium niobate glass ceramic material comprises the steps:
1) by SrCO
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2mix according to 12:12:24:10:10:30:3, obtain mixture;
2) quartz crucible during from room temperature to 1100 ℃, is started to add mixture with stove heating, then continue to be heated to 1350 ℃, and at 1350 ℃, be incubated 30min and make mixture melting even, obtain mixed melting material; By the moulding on copper coin of mixed melting material, then put into rapidly the stove 7h that anneals, glass after being annealed at 600 ℃;
3) do the test of DTA differential thermal analysis by glass grinding powder after the annealing that takes a morsel, after being annealed, the crystallization temperature of glass is 1035 ℃, at this temperature, be incubated 4h and carry out crystallization processing, then furnace cooling, to room temperature, obtains block strontium barium niobate glass ceramic material.
The strontium barium niobate glass-ceramic cutting machine that the present embodiment is obtained is switched to the thin slice that thickness is 0.1-0.2mm, and thin slice, after polishing, cleaning, evenly applies silver electrode paste at thin slice tow sides, in 600 ℃ of sintering 20 minutes, obtains glass-ceramic sample to be measured.
Embodiment 2:
The present embodiment strontium barium niobate glass ceramic material comprises that mol ratio is SrO, BaO, the Nb of 12:12:24:12:12:18:3
2o
5, CaO, SiO
2, B
2o
3and BaF
2.
The SrCO that the present embodiment strontium barium niobate glass ceramic material is is 12:12:24:12:12:36:3 by mol ratio
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2make through melting, moulding, annealing and crystallization processing.
The preparation method of the present embodiment strontium barium niobate glass ceramic material comprises the steps:
1) by SrCO
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2mix according to 12:12:24:12:12:36:3, obtain mixture;
2) while quartz crucible being heated to 1100 ℃ from room temperature with stove, start to add mixture, then continue to be heated to 1350 ℃, and at 1350 ℃, be incubated 30min and make mixture melting even, obtain mixed melting material; By the moulding on copper coin of mixed melting material, then put into rapidly the stove 7h that anneals, glass after being annealed at 600 ℃;
3) do the test of DTA differential thermal analysis by glass grinding powder after the annealing that takes a morsel, after being annealed, the crystallization temperature of glass is 973 ℃, at this temperature, be incubated 4h and carry out crystallization processing, then cool to room temperature with the furnace, obtain block strontium barium niobate glass ceramic material.
The strontium barium niobate glass-ceramic cutting machine that the present embodiment is obtained is switched to the thin slice that thickness is 0.1-0.2mm, and thin slice, after polishing, cleaning, evenly applies silver electrode paste at thin slice tow sides, in 600 ℃ of sintering 20 minutes, obtains glass-ceramic sample to be measured.
Embodiment 3:
The present embodiment strontium barium niobate glass ceramic material comprises that mol ratio is SrO, BaO, the Nb of 12:12:24:14:14:21:3
2o
5, CaO, SiO
2, B
2o
3and BaF
2.
The SrCO that the present embodiment strontium barium niobate glass ceramic material is is 12:12:24:14:14:42:3 by mol ratio
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2make through melting, moulding, annealing and crystallization processing.
The preparation method of the present embodiment strontium barium niobate glass ceramic material comprises the steps:
1) by SrCO
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2mixed in molar ratio according to 12:12:24:14:14:42:3 is even, obtains mixture;
2) while quartz crucible being heated to 1100 ℃ from room temperature with stove, start to add mixture, then continue to be heated to 1350 ℃, and at 1350 ℃, be incubated 30min and make mixture melting even, obtain mixed melting material; By the moulding on copper coin of mixed melting material, then put into rapidly the stove 7h that anneals, glass after being annealed at 600 ℃;
3) do the test of DTA differential thermal analysis by glass grinding powder after the annealing that takes a morsel, after being annealed, the crystallization temperature of glass is 935 ℃, at this temperature, be incubated 4h and carry out crystallization processing, then cool to room temperature with the furnace, obtain block strontium barium niobate glass ceramic material;
The strontium barium niobate glass-ceramic cutting machine that the present embodiment is obtained is switched to the thin slice that thickness is 0.1-0.2mm, and thin slice, after polishing, cleaning, evenly applies silver electrode paste at thin slice tow sides, in 600 ℃ of sintering 20 minutes, obtains glass-ceramic sample to be measured.
As shown in Figure 1, in this embodiment 3, generated very pure Strontium Barium Niobate Crystal, and amount of crystals is large, meanwhile, has a small amount of SiO
2crystal is separated out.As in Figure 2-4, in the SEM photo of the prepared strontium barium niobate glass-ceramic of embodiment 3 and EDS photo, the relatively dark peach blossom shape of color is SiO
2, other are Strontium Barium Niobate Crystal.Peach blossom shape SiO
2evenly generate, show that strontium barium niobate glass-ceramic inner glass and ferroelectric Strontium Barium Niobate Crystal are uniformly distributed, it is minimum that scorification is prepared glass-ceramic void content.
Embodiment 4:
The present embodiment strontium barium niobate glass ceramic material comprises that mol ratio is SrO, BaO, the Nb of 12:12:24:16:16:24:3
2o
5, CaO, SiO
2, B
2o
3and BaF
2.
The SrCO that the present embodiment strontium barium niobate glass ceramic material is is 12:12:24:16:16:48:3 by mol ratio
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2make through melting, moulding, annealing and crystallization processing.
The preparation method of the present embodiment strontium barium niobate glass ceramic material comprises the steps:
1) by SrCO
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
212:12:24:16:16:48:3 mole mixes, and obtains mixture;
2) while quartz crucible being heated to 1100 ℃ from room temperature with stove, start to add mixture, then continue to be heated to 1350 ℃, and at 1350 ℃, be incubated 30min and make mixture melting even, obtain mixed melting material; By the moulding on copper coin of mixed melting material, then put into rapidly the stove 7h that anneals, glass after being annealed at 600 ℃;
3) by doing the test of DTA differential thermal analysis after glass grinding powder after a small amount of annealing, after being annealed, the crystallization temperature of glass is 875 ℃, at this temperature, be incubated 4h and carry out crystallization processing, then cool to room temperature with the furnace, obtain block strontium barium niobate glass ceramic material.
The strontium barium niobate glass-ceramic cutting machine that the present embodiment is obtained is switched to the thin slice that thickness is 0.1-0.2mm, and thin slice, after polishing, cleaning, evenly applies silver electrode paste at thin slice tow sides, in 600 ℃ of sintering 20 minutes, obtains glass-ceramic sample to be measured.
The dielectric properties test data (1kHz) of glass-ceramic sample to be measured prepared by table one
According to energy storage formula:
ε
0for dielectric constant of air, ε
rfor the specific inductivity of glass-ceramic sample to be measured, E
bfor breaking down field strength; Breaking down field strength is to affect one of the most significant factor of energy storage density, glass ceramic material is because of the reduced dielectric constant that exists of glass, breaking down field strength increases, as can be seen from Table 1, the present invention is by rationally controlling the ratio of ferroelectric Strontium Barium Niobate Crystal and glass content, the ferroelectric glass-ceramic of the generation high breaking down field strength of high-k and low dielectric loss.Scorification preparation method is easy, and forming method is more, and resistance to disruptive strength is high, is the important method of preparing high energy storage density material.The strontium barium niobate glass-ceramic of the high breaking down field strength of high-k prepared by this invention is expected to substitute conventional iron electroceramics material becomes one of double excellent technically and economically important candidate material of energy storage material.
Embodiment 5:
The present embodiment strontium barium niobate glass ceramic material comprises that mol ratio is SrO, BaO, the Nb of 12:12:24:12:12:18:3
2o
5, CaO, SiO
2, B
2o
3and BaF
2.
The SrCO that the present embodiment strontium barium niobate glass ceramic material is is 12:12:24:12:12:36:3 by mol ratio
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2make through melting, moulding, annealing and crystallization processing.
The preparation method of the present embodiment strontium barium niobate glass ceramic material comprises the steps:
1) by SrCO
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2mix according to 12:12:24:12:12:36:3, obtain mixture;
2) while quartz crucible being heated to 1100 ℃ from room temperature with stove, start to add mixture, then continue to be heated to 1300 ℃, and at 1300 ℃, be incubated 30min and make mixture melting even, obtain mixed melting material; By the moulding on copper coin of mixed melting material, then put into rapidly the stove 6.5h that anneals, glass after being annealed at 680 ℃;
3) do the test of DTA differential thermal analysis by glass grinding powder after the annealing that takes a morsel, after being annealed, the crystallization temperature of glass is 973 ℃, at this temperature, be incubated 3h and carry out crystallization processing, then cool to room temperature with the furnace, obtain block strontium barium niobate glass ceramic material.
Embodiment 6:
The present embodiment strontium barium niobate glass ceramic material comprises that mol ratio is SrO, BaO, the Nb of 12:12:24:16:16:24:3
2o
5, CaO, SiO
2, B
2o
3and BaF
2.
The SrCO that the present embodiment strontium barium niobate glass ceramic material is is 12:12:24:16:16:48:3 by mol ratio
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2make through melting, moulding, annealing and crystallization processing.
The preparation method of the present embodiment strontium barium niobate glass ceramic material comprises the steps:
1) by SrCO
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
212:12:24:16:16:48:3 mole mixes, and obtains mixture;
2) while quartz crucible being heated to 1100 ℃ from room temperature with stove, start to add mixture, then continue to be heated to 1400 ℃, and at 1400 ℃, be incubated 30min and make mixture melting even, obtain mixed melting material; By the moulding on copper coin of mixed melting material, then put into rapidly the stove 4h that anneals, glass after being annealed at 800 ℃;
3) by doing the test of DTA differential thermal analysis after glass grinding powder after a small amount of annealing, after being annealed, the crystallization temperature of glass is 875 ℃, at this temperature, be incubated 6h and carry out crystallization processing, then cool to room temperature with the furnace, obtain block strontium barium niobate glass ceramic material.
The foregoing is only one embodiment of the present invention, it not whole or unique embodiment, the conversion of any equivalence that the logical technician in this area takes technical solution of the present invention by reading specification sheets of the present invention, is claim of the present invention and contains.
Claims (8)
1. a strontium barium niobate glass ceramic material for the high breaking down field strength of high-k, is characterized in that: comprise that mol ratio is SrO, BaO, the Nb of 12:12:24:2x:2x:3x:3
2o
5, CaO, SiO
2, B
2o
3and BaF
2, and x=5～8.
2. a strontium barium niobate glass ceramic material for the high breaking down field strength of high-k, is characterized in that: the SrCO that this strontium barium niobate glass ceramic material is is 12:12:24:2x:2x:6x:3 by mol ratio
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2make through melting, moulding, annealing and crystallization processing.
3. a preparation method for the strontium barium niobate glass ceramic material of the high breaking down field strength of high-k, is characterized in that, comprises the steps:
1) by SrCO
3, BaCO
3, Nb
2o
5, CaCO
3, SiO
2, H
3bO
3and BaF
2according to 12SrO-12BaO-24Nb
2o
3-2xCaO-2xSiO
2-3xB
2o
3-3BaF
2mixed in molar ratio is even, obtains mixture; Wherein, x=5～8;
2) crucible is heated to 1100 ℃ with stove, starts to add mixture, then continue to be heated to 1300-1400 ℃, at 1300-1400 ℃, insulation makes mixture melting even, obtains mixed melting material; By the moulding on mould of mixed melting material, then put into stove and anneal at 600-800 ℃, glass after being annealed;
3) after annealing, glass is incubated and carries out crystallization processing under its crystallization temperature, obtains strontium barium niobate glass ceramic material.
4. the preparation method of the strontium barium niobate glass ceramic material of the high breaking down field strength of high-k according to claim 3, is characterized in that: x=5,6,7 or 8 in described step 1).
5. the preparation method of the strontium barium niobate glass ceramic material of the high breaking down field strength of high-k according to claim 3, is characterized in that: the crystallization temperature in described step 3) is determined glass after annealing through the test of DTA differential thermal analysis.
6. the preparation method of the strontium barium niobate glass ceramic material of the high breaking down field strength of high-k according to claim 5, is characterized in that: in the time of x=5, after annealing, the crystallization temperature of glass is 1035 ℃; In the time of x=6, after annealing, the crystallization temperature of glass is 973 ℃; In the time of x=7, after annealing, the crystallization temperature of glass is 935 ℃; In the time of x=8, after annealing, the crystallization temperature of glass is 875 ℃.
7. the preparation method of the strontium barium niobate glass ceramic material of the high breaking down field strength of high-k according to claim 3, is characterized in that: in described step 3), the crystallization treatment time is 3-6h.
8. the preparation method of the strontium barium niobate glass ceramic material of the high breaking down field strength of high-k according to claim 3, is characterized in that: described step 2) in annealing time be 4-7h.
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