CN1569731A - Li-Si-O-based high dielectric constant ceramic materials and method for synthesizing same - Google Patents
Li-Si-O-based high dielectric constant ceramic materials and method for synthesizing same Download PDFInfo
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- CN1569731A CN1569731A CN 200410034110 CN200410034110A CN1569731A CN 1569731 A CN1569731 A CN 1569731A CN 200410034110 CN200410034110 CN 200410034110 CN 200410034110 A CN200410034110 A CN 200410034110A CN 1569731 A CN1569731 A CN 1569731A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- 229910008373 Li-Si-O Inorganic materials 0.000 title abstract 2
- 229910006757 Li—Si—O Inorganic materials 0.000 title abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000009388 chemical precipitation Methods 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 18
- 229910018553 Ni—O Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000001879 gelation Methods 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 8
- 235000012501 ammonium carbonate Nutrition 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 150000003841 chloride salts Chemical class 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229910021653 sulphate ion Inorganic materials 0.000 abstract 1
- 229910013553 LiNO Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910004247 CaCu Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910002659 PbMg1/3Nb2/3O3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Inorganic Insulating Materials (AREA)
Abstract
The invention relates to a Li-Si-O-based high dielectric constant ceramic materials and method for synthesizing same, wherein the raw material includes Ni, Li sulphate, nitrate or chloride salt, the preparation consists of using ammonium carbonate or ammonium acid carbonate as precipitation reagent, synthesizing uniformly doped nano precursor powder through chemical precipitation method or sol-gal process, granulating, modeling, sintering, thus obtaining lithium, silicon doped nickel protoxide ceramics.
Description
Technical field
The present invention relates to a kind of novel Li-Si-Ni-O base high dielectric constant ceramic material and synthetic method thereof, belong to the oxide ceramic material preparing technical field.
Background technology
Along with electronic information technology, the continuous development of particularly mixed unicircuit and surface mounting technology, the new function ceramic components more and more receives publicity, and its development trend is mainly reflected in the microminiaturization of device, integrated, chip type, high frequencyization, high reliability.Wherein the ceramic condenser of ceramic condenser, particularly high specific volume develops over past ten years rapidly as a class important electron element, and its market demand grows with each passing day.High-performance, high specific volume, microminiaturization, low cost are the trend of ceramic condenser element development.
At present, existing high dielectric constant material mostly is perovskite structure, as ferroelectrics (as Pb (Zr, Ti) O
3) and relaxation ferroelectric (as PbMg
1/3Nb
2/3O
3), its specific inductivity can reach several thousand even up to ten thousand.Kim research group has reported the PbTiO of La modification
3The base pottery, by control PbO amount, sintering in oxidizing atmosphere forms a large amount of Pb rooms, the PbTiO of the final doping 15%La that obtains
3Material dielectric constant is high unusually, reaches about 65000 during room temperature.Though above-mentioned materials has higher dielectric constant, its dielectric constant with temperature can change a lot, and this shortcoming has limited the application of these materials greatly, has reduced the stability of device.And majority all contains lead in these materials, contaminate environment, infringement HUMAN HEALTH.People such as Homes find CaCu
3Ti
4O
12Have unusual high specific inductivity, can reach 10
4During low temperature, specific inductivity is bigger with frequency change, and dielectric loss is also bigger, difficult synthetic pure CaCu
3Ti
4O
12Phase.In addition, boundary layer capacitorl (BLC) and multi-layer capacitor (MLCC) also cause the interest that people are bigger.These electrical condensers mainly are the BaTiO of modification
3Base ferroelectric ceramic(s) and some other titanate are made the sintering temperature of this type of material higher (usually more than 1300 ℃).Studied CuO to (Ba as people such as Yang
1-xSr
x) (Ti
0.9Zr
0.1) O
3Different CuO, Sr content and firing temperature are found in the influence of dielectric properties, and very big to the specific inductivity influence of this BLC, its specific inductivity changes at 2870-22370, and CuO plays and suppresses grain growth, acceleration of sintering, and accumulates in the crystal boundary place.Chio etc. add SiO
2, Nb
2O
5, Dy
2O
3To BaTiO
3In, by 1350 ℃ of control sintering atmospheres, utilize three kinds of atmosphere to BaTiO
3The crystal grain semiconductor.At 750 ℃ sample is carried out partial oxidation then, thereby obtain the boundary layer capacitorl that specific inductivity under the 1kHz reaches 2000-346000.This type of boundary layer capacitorl preparation technology more complicated need strictly be controlled firing atmosphere or add the thickness that oxide compound is controlled semiconductor and the second insulation phase mutually layer of crystal grain.Because the sintering temperature height needs to use a large amount of precious metals such as palladium, platinum etc. as inner electrode, its cost accounts for more than 60% of MLC total cost, thereby makes the MLC cost can not be in any more, has influenced its development.The specific inductivity of this material and loss are generally obvious with temperature and frequency change, thereby have limited its application.Recently, Carlos Pecharroman has reported a kind of high-K capacitor based on the seep effect preparation.They utilize BaTiO
3Doping metals Ni powder, at 1350 ℃ of sintering, its specific inductivity of composite dielectric body material of acquisition can reach about 80000.People such as Duan find to control certain firing condition by metal Pt particle is joined among the PZT, and its dielectric properties also can be significantly improved.Recently, we have unusual high specific inductivity (ε＞10 by nickel oxide being carried out Li and Ti doped (Li-Ti-Ni-O) series ceramic material that obtains
4, at f=10～10MHz), and temperature stability is good, is a kind of novel no Pb huge dielectric constant material.But, discover that though its specific inductivity of this dielectric materials is very high, its loss also can be in any more.
Summary of the invention
The novel NiO base high dielectric ceramic that the purpose of this invention is to provide a kind of high dielectric, low-loss, good stability.Promptly by chemical precipitation method or the synthetic even adulterated nanometer presoma body powder of sol-gel method, by granulation, moulding, certain technology sintering, can obtain lithium, silicon coblended nickel oxide pottery, it has high-k and good temperature stability, and be lead-free systems, with respect to the NiO base pottery of former Li, Ti codoped, its loss descends significantly, is the novel dielectric materials that a class has broad prospect of application.
A kind of Li-Si-Ni-O base high dielectric constant ceramic material and synthetic method thereof that the present invention proposes, it is characterized in that: described material feedstock adopts vitriol, nitrate or the muriate salt of Ni, Li, with volatile salt or bicarbonate of ammonia as precipitation agent, by chemical precipitation method or the synthetic even adulterated nanometer presoma powder of sol-gel method, through granulation, moulding, sintering, obtain lithium, silicon coblended nickel oxide pottery.
The synthetic method of a kind of Li-Si-Ni-O base high dielectric constant ceramic material that the present invention proposes, it is characterized in that: described method is carried out successively as follows:
(1) is that 1: 0.001～0.15 molar ratio ingredient is weighed by Ni/Li, is made into certain density solution;
(2) the Ni/Li mixed solution with step (1) joins in the volatile salt or ammonium bicarbonate soln that concentration is 0.1～0.5mol/L, and it is fully reacted;
(3) the throw out washing that step (2) is obtained, drying, the nano level NiO presoma powder of acquisition Li doped;
(4) above-mentioned presoma powder is dispersed in the distilled water, forms suspension, add teos solution, regulator solution pH value is 4～8, makes teos hydrolysis, is coated on the Ni/Li powder, forms composite granule;
(5) composite granule filtration, washing, the drying that step (4) is obtained, granulation, dry-pressing formed under 2～6Mpa, sintering is 2～4 hours in 1150～1300 ℃ of air, is Li-Si-Ni-O base high dielectric constant ceramic material.
In the synthetic method of above-mentioned Li-Si-Ni-O base high dielectric constant ceramic material, the first regulator solution pH of described step (4) value makes teos hydrolysis form colloidal sol, and the mixed solution with Ni/Li slowly joins in this colloidal sol then, further gelation.
In the synthetic method of above-mentioned Li-Si-Ni-O base high dielectric constant ceramic material, described step (5) obtains Li-Si-Ni-O base high dielectric constant ceramic material with sintering in xerogel pre-burning, granulation, dry-pressing formed under 2～6Mpa, 1100～1300 ℃ of air 2～5 hours.
The present invention can regulate and control the dielectric properties (as specific inductivity, dielectric loss and temperature stability) of this material system by changing different doped elements and relative doping content.Adopt chemical precipitation method or sol-gel method, can obtain that particle diameter is controlled, the uniform active nano presoma of chemical ingredients powder, thereby can reduce ceramic sintering temperature, shorten the reaction times, cut down the consumption of energy, improve product performance.
Description of drawings
Fig. 1 is the XRD figure spectrum of product in the embodiment of the invention 1.
Fig. 2 is the specific inductivity of product in the embodiment of the invention 1 and the graph of a relation of frequency.
Fig. 3 is the microscopic appearance of product in the embodiment of the invention 1.
Fig. 4 is the XRD figure spectrum of product in the embodiment of the invention 2.
Fig. 5 is the specific inductivity of product in the embodiment of the invention 2 and the graph of a relation of frequency.
Fig. 6 is the XRD figure spectrum of product in the embodiment of the invention 3.
Fig. 7 is the specific inductivity of product in the embodiment of the invention 3 and the graph of a relation of frequency.
Fig. 8 is the specific inductivity of product in the embodiment of the invention 3 and the graph of a relation of temperature.
Fig. 9 is the specific inductivity of product in the embodiment of the invention 4 and the graph of a relation of frequency.
Figure 10 is the specific inductivity of product in the embodiment of the invention 5 and the graph of a relation of frequency.
Embodiment
The present invention will be further described below by embodiment:
Embodiment 1:
Weighing 0.005mol LiNO
3, 0.965mol Ni (NO
3)
2Be dissolved in the 500ml deionized water, be made into the Li/Ni mixed solution, the mixed liquid of this Ni/Li is slowly joined in the ammonium bicarbonate soln of 0.5mol/L, it is fully reacted, with the throw out washing, dry under 100 ℃ then, the nano level NiO presoma powder of acquisition Li doped.This composite granule is dispersed in the distilled water, forms suspension, slowly add teos solution and (contain 0.03mol SiO approximately
2), regulator solution pH value is about about 7.5, makes teos hydrolysis, is coated on the Ni/Li powder, forms a coating layer.With this composite granule filtration, washing, drying,, obtain Li by sintering in granulation, dry-pressing formed under 3MPa, the 1250 ℃ of air 2.5 hours
0.005Si
0.03Ni
0.965The O stupalith.XRD test shows, thing are the NiO phase mutually substantially.Under the room temperature, relative permittivity ε=10200 (1kHz), specific inductivity is little with frequency change.The microstructure picture of material shows that the grain size of pottery is more even.As Fig. 1, Fig. 2, shown in Figure 3.
Embodiment 2
With teos solution (about 0.15mol SiO
2), regulator solution pH value is about about 3.5, makes teos hydrolysis, forms vitreosol.Weighing 0.01mol LiNO
3, 0.84mol Ni (NO
3)
2Be dissolved in the 400ml deionized water, be made into the Li/Ni mixed solution, the mixed liquid of this Ni/Li is slowly joined in this colloidal sol, regulate pH value about about 7.2, make its further gelation, xerogel 300 ℃ of following pre-burnings, is obtained the nano level NiO presoma powder of Li doped.With sintering in this pre-burning powder granulation, dry-pressing formed under 4MPa, the 1250 ℃ of air 2.5 hours, obtain Li
0.01Si
0.15Ni
0.84The O stupalith.XRD test shows, thing major part mutually are the NiO phase, also have small amount of N i
2SiO
4Phase.Under the room temperature, relative permittivity ε=1890 (10kHz), dielectric loss tan δ=0.42.As Fig. 4, shown in Figure 5.
Embodiment 3
Weighing 0.01mol LiNO
3, 0.79mol Ni (NO
3)
2Be dissolved in the 400ml deionized water, be made into the Li/Ni mixed solution, the mixed liquid of this Ni/Li is slowly joined in the sal volatile of 0.8mol/L, it is fully reacted, with the throw out washing, dry under 70 ℃ then, the nano level NiO presoma powder of acquisition Li doped.This composite granule is dispersed in the distilled water, forms suspension, slowly add teos solution (about 0.20mol SiO
2), regulator solution pH value is about about 7.8, makes teos hydrolysis, is coated on the Ni/Li powder, forms a coating layer.With this composite granule filtration, washing, drying,, obtain Li by sintering in granulation, dry-pressing formed under 3MPa, the 1250 ℃ of air 2.5 hours
0.01Si
0.2Ni
0.79The O stupalith.XRD test shows, thing major part mutually are the NiO phase, also have small amount of N i
2SiO
4Phase.Under the room temperature, relative permittivity ε=870 (10kHz), dielectric loss tan δ=0.35.And in-10 ℃ of-170 ℃ of temperature ranges, dielectric constant with temperature changes less.As Fig. 6, Fig. 7 and shown in Figure 8.
Weighing 0.012mol LiNO
3, 0.96mol NiCl
2Be dissolved in the 500ml deionized water, be made into the Li/Ni mixed solution, the mixed liquid of this Ni/Li is slowly joined in the sal volatile of 0.5mol/L, it is fully reacted, with the throw out washing, dry under 90 ℃ then, the nano level NiO presoma powder of Li is mixed in acquisition.This composite granule is dispersed in the distilled water, forms suspension, slowly add teos solution (about 0.028mol SiO
2), regulator solution pH value is about about 6.5, makes teos hydrolysis, is coated on the Ni/Li powder, forms a coating layer.With this composite granule filtration, washing, drying,, obtain Li by sintering in granulation, dry-pressing formed under 5MPa, the 1200 ℃ of air 3.0 hours
0.010Si
0.028Ni
0.96The O stupalith.XRD test shows, thing are the NiO phase mutually substantially.Under the room temperature, relative permittivity ε=26700 (10kHz), dielectric loss tan δ=0.65.Shown in Figure 9.
Embodiment 5
With teos solution (about 0.15mol SiO
2), regulator solution pH value is about about 4.0, makes teos hydrolysis, forms vitreosol.Weighing 0.012mol LiNO
3, 0.838mol Ni (NO
3)
2Be dissolved in the 400ml deionized water, be made into the Li/Ni mixed solution, the mixed liquid of this Ni/Li is slowly joined in this colloidal sol, it is about 4.0 to regulate the pH value, makes its further gelation, and xerogel 350 ℃ of following pre-burnings, is obtained the nano level NiO presoma powder of Li doped.With sintering in this pre-burning powder granulation, dry-pressing formed under 6MPa, the 1300 ℃ of air 2.0 hours, obtain Li
0.012Si
0.15Ni
0.838The O stupalith.XRD test shows, thing major part mutually are the NiO phase, also have small amount of N i
2SiO
4Phase.Under the room temperature, relative permittivity ε=11200 (10kHz), dielectric loss tan δ=0.45.As shown in figure 10.
Claims (4)
1, a kind of Li-Si-Ni-O base high dielectric constant ceramic material and synthetic method thereof, it is characterized in that: described material feedstock adopts vitriol, nitrate or the muriate salt of Ni, Li, with volatile salt or bicarbonate of ammonia as precipitation agent, by chemical precipitation method or the synthetic even adulterated nanometer presoma powder of sol-gel method, through granulation, moulding, sintering, obtain lithium, silicon coblended nickel oxide pottery.
2, a kind of method of synthetic Li-Si-Ni-O base high dielectric constant ceramic material as claimed in claim 1, it is characterized in that: described method is carried out successively as follows:
(1) is that 1: 0.001～0.15 molar ratio ingredient is weighed by Ni/Li, is made into certain density solution;
(2) the Ni/Li mixed solution with step (1) joins in the volatile salt or ammonium bicarbonate soln that concentration is 0.1～0.5mol/L, and it is fully reacted;
(3) the throw out washing that step (2) is obtained, drying, the nano level NiO presoma powder of acquisition Li doped;
(4) above-mentioned presoma powder is dispersed in the distilled water, forms suspension, add teos solution, regulator solution pH value is 4～8, makes teos hydrolysis, is coated on the Ni/Li powder, forms composite granule;
(5) composite granule filtration, washing, the drying that step (4) is obtained, granulation, dry-pressing formed under 2～6MPa, sintering is 2～4 hours in 1150～1300 ℃ of air, is Li-Si-Ni-O base high dielectric constant ceramic material.
3, according to the method for the described Li-Si-Ni-O of claim 1 base high dielectric constant ceramic material, it is characterized in that: the first regulator solution pH of described step (4) value, make teos hydrolysis form colloidal sol, the mixed solution with Ni/Li slowly joins in this colloidal sol then, further gelation.
4, according to the method for claim 1 or 3 described Li-Si-Ni-O base high dielectric constant ceramic materials, it is characterized in that: described step (5) obtains Li-Si-Ni-O base high dielectric constant ceramic material with sintering in xerogel pre-burning, granulation, dry-pressing formed under 2～6MPa, 1100～1300 ℃ of air 2～5 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1971783B (en) * | 2006-12-04 | 2010-11-24 | 天津大学 | Barium titanate based metal-dielectric composite ceramic capacitor medium and its preparing method |
| CN101980984B (en) * | 2008-03-20 | 2015-11-25 | 旭硝子欧洲玻璃公司 | Cover lamellate glass |
| CN106278242A (en) * | 2016-07-19 | 2017-01-04 | 桂林理工大学 | Low-loss temperature-stabilized microwave dielectric ceramic LiFeSn3o8 |
| WO2017120990A1 (en) * | 2016-01-13 | 2017-07-20 | 广东工业大学 | Process for preparing net-size, complex-shape transparent ceramic piece |
| CN112151268A (en) * | 2019-06-28 | 2020-12-29 | 株式会社村田制作所 | Laminated electronic component |
| CN114939419A (en) * | 2022-06-27 | 2022-08-26 | 中国科学院赣江创新研究院 | Palladium-based catalyst containing silicon-doped nickel oxide carrier and preparation method and application thereof |
-
2004
- 2004-04-23 CN CN 200410034110 patent/CN1569731A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1971783B (en) * | 2006-12-04 | 2010-11-24 | 天津大学 | Barium titanate based metal-dielectric composite ceramic capacitor medium and its preparing method |
| CN101980984B (en) * | 2008-03-20 | 2015-11-25 | 旭硝子欧洲玻璃公司 | Cover lamellate glass |
| WO2017120990A1 (en) * | 2016-01-13 | 2017-07-20 | 广东工业大学 | Process for preparing net-size, complex-shape transparent ceramic piece |
| CN106278242A (en) * | 2016-07-19 | 2017-01-04 | 桂林理工大学 | Low-loss temperature-stabilized microwave dielectric ceramic LiFeSn3o8 |
| CN112151268A (en) * | 2019-06-28 | 2020-12-29 | 株式会社村田制作所 | Laminated electronic component |
| CN114939419A (en) * | 2022-06-27 | 2022-08-26 | 中国科学院赣江创新研究院 | Palladium-based catalyst containing silicon-doped nickel oxide carrier and preparation method and application thereof |
| CN114939419B (en) * | 2022-06-27 | 2023-10-13 | 中国科学院赣江创新研究院 | Palladium-based catalyst containing silicon-doped nickel oxide carrier, and preparation method and application thereof |
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