CN101891463B - Dielectric adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material and preparation method thereof - Google Patents
Dielectric adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material and preparation method thereof Download PDFInfo
- Publication number
- CN101891463B CN101891463B CN 201010206295 CN201010206295A CN101891463B CN 101891463 B CN101891463 B CN 101891463B CN 201010206295 CN201010206295 CN 201010206295 CN 201010206295 A CN201010206295 A CN 201010206295A CN 101891463 B CN101891463 B CN 101891463B
- Authority
- CN
- China
- Prior art keywords
- dielectric
- barium
- dielectric material
- tio
- adjustable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a dielectric adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material and a preparation method thereof, belonging to the technical field of electronic materials and devices. The doped ceramic-dielectric material comprises the following components in percentage by weight: x% of A, (1-x%)*y% of Bal-zSrzTiO3 and (1-x%)*(1-y%) of BaWO4, wherein A is selected from V2O5, Cr2O3, MnCO3 and Co2O3 or NiF2; x% is more than 0wt% and less than 5wt%, y% is more than or equal to 5wt% and less than or equal to 95wt%, and z is more than or equal to 0.4 and less than or equal to 0.6. The ceramic-dielectric material has high Q value, low dielectric constant and very high dielectric adjustable rate and can be widely used for preparing adjustable microwave components, i.e. an electric tuning microwave resonator, a filter, a microwave dielectric antenna, and the like.
Description
Technical field
The invention belongs to electronic material and device technology field, be specifically related to adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material of a kind of dielectric and preparation method thereof.
Background technology
Have high-k, low-dielectric loss, nonlinear dielectric constant is adjustable with and the adjustable perovskite structure strontium-barium titanate ferroelectric material of Curie temperature aspect microwave adjustable device (such as phase shifter, wave filter, variable condenser and retarding line etc.) obtain increasingly extensive concern, especially at the present focus of research especially aspect microwave phase shifter.But the BST stupalith with high-k is difficult to satisfy itself and driving source internal impedance match and high-power requirement, and this has limited its application in the microwave adjustable device field greatly.The Q value is to weigh the significant parameter of inductance component, when the Q value refers to that inducer is worked under the voltage of alternating current of a certain frequency, and the ratio of the induction reactance that presents loss resistance equivalent with it.The Q value of inducer is higher, and its loss is less, and efficient is higher.The specific inductivity of strontium-barium titanate BST material changes with the variation of applying direct current electric field, and when voltage changes to V (app) from V (0), specific inductivity will produce an increment Delta ε
r=[ε
R (0)-ε
R (app)], this increment and ε
R (0)The percentage ratio of ratio become adjustability, namely use Tunability (being abbreviated as T)=[ε
R (0)-ε
R (app)]/ε
R (0)* 100% represents.And will produce corresponding differential phase shift when applying simultaneously the light (microwave) of a particular frequencies, reach the purpose that changes phase place.Material with this specific character becomes electrooptical material.The ability that phase shifter changes the phasing degree is mainly decided by adjustability, so high adjustability is very important for the phase shifter material.
Therefore, how to prepare both had low-k, high Q value, the material system that has again high dielectric tunable characteristic is technological difficulties.
Doping vario-property to Ceramic Composite is that the electron ceramic material modification is comparatively commonly used and one of effective means, material doped by the different mass ratio, to enter in the crystalline network of crystalline material with different modes in various degree, cause the change of material microstructure, thereby effectively adjust and improve the correlated performance of material.In the prior art, the researchist adopts La
2O
3Doping Ba
0.6Sr
0.4TiO
3+ MgO, B
2O
3Doping Ba
0.6Sr
0.4TiO
3+ MgO, MgO doping Ba
0.6Sr
0.4TiO
3+ Mg
2SiO
4, MgO doping Ba
0.4Sr
0.6TiO
3+ MgAl
2O
4, MgO+MnCO
3Doping Ba
0.4Sr
0.6TiO
3+ MgAl
2O
4Etc. system, development obtains having low-k, the ceramic medium material system of high Q value and high dielectric tunable characteristic.The people such as the Xiaohong Wang of the Central China University of Science and Technology compare La to the difference amount
2O
3Doping Ba
0.6Sr
0.4TiO
3+ MgO has carried out systematic research, obtains microwave ceramic dielectric material (ε
r=94.05, δ=0.012～2.853GHz, T=16.26%).Yet the micro-wave dielectric tunable characteristic research of transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material there is not yet relevant report.This seminar finds that on the basis of original research BST+BaWO4 composite ceramic body cording has moderate specific inductivity and very high dielectric adjustable energy, but the problem that exists is that loss is excessive under microwave frequency band, and the Q value is less than normal, does not reach 100; BST+ZnWO4 composite ceramic body cording has low-k and very high Q value, but the problem that exists is that the dielectric adjustable energy is little, is no more than 10%.Can obtain all microwave dielectric properties of good good combination property of low specific inductivity, high Q value and tunable performance by further this compound system being carried out doping vario-property.
Summary of the invention
The purpose of this invention is to provide adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material of a kind of dielectric and preparation method thereof, the transition metal element compound doped barium-strontium titanate based composite tungstate ceramic medium material that this dielectric is adjustable has high Q value, low-k and the high excellent micro-wave dielectric over-all propertieies such as the adjustable rate of dielectric.
Component and the weight percentage of the transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material that dielectric of the present invention is adjustable are:
A x％
Ba
1-zSr
zTiO
3 (1-x％)*y％
BaWO
4 (1-x％)*(1-y％)
Wherein, A is selected from V
2O
5, Cr
2O
3, MnCO
3, Co
2O
3Or NiF
2X% is weight percentage, and span is 0wt%＜x%＜5wt%; Y% is weight percentage, and span is 5wt%≤y%≤95wt%; The span of z is 0.4≤z≤0.6.
Better, the span of described x% is 0.05wt%≤x%≤1wt%, more preferably 0.1wt%≤x%≤0.3wt%; The span of described y% is 35wt%≤y%≤65wt%, more preferably 45wt%≤y%≤55wt%.
Preferred, described x%=0.2%, y%=50%, z=0.5.
The more preferably component that is the adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material of described dielectric is: 0.2%A+49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4, wherein, A is selected from V
2O
5, Cr
2O
3, MnCO
3, Co
2O
3Or NiF
2
The component expression x%A+[(1-x% of the transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material that described dielectric is adjustable) * y%] Ba
1-zSr
zTiO
3+ [(1-x%) * (1-y%)] BaWO
4In, the mole number of each corresponding element of digitized representation in the element lower right corner; The x% representative is in the total mass of described transition metal element compound doped barium-strontium titanate compound-barium tungstate stupalith, the mass percent of described A; (1-x%) * y% representative is in the total mass of described transition metal element compound doped barium-strontium titanate compound-barium tungstate stupalith, described Ba
1-zSr
zTiO
3Mass percent; (1-x%) * (1-y) % representative is in the total mass of described transition metal element compound doped barium-strontium titanate compound-barium tungstate stupalith, described BaWO
4Mass percent.
The transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material preparation method that dielectric of the present invention is adjustable specifically comprises the steps:
1) adopt solid-phase synthesis to prepare mixed powder, concrete steps are: select A powder, BaCO
3Powder, SrCO
3Powder, TiO
2Powder and WO
3Powder is as main raw material, according to x%A+[(1-x%) * y%] Ba
1-zSr
zTiO
3+ [(1-x%) * (1-y%)] BaWO
4In the molar ratio ingredient of various elements, add zirconia ball and ball-milling medium in the mixing raw material for preparing, after ball milling and the discharging oven dry, obtain mixed powder through pre-burning and grinding again;
2) in step 1) in add zirconia ball and ball-milling medium in the mixed powder that makes, sieve after ball milling and the discharging oven dry;
3) adopt binding agent to step 2) in powder after sieving carry out granulation, under 10MPa～100MPa pressure, be pressed into the ceramic green sheet;
4) with step 3) in the ceramic green sheet that makes carry out sintering through row is sticking after processing, can obtain described transition metal element compound doped barium-strontium titanate composite tungstate ceramic medium material.
Described step 1) A in is selected from V
2O
5, Cr
2O
3, MnCO
3, Co
2O
3Or NiF
2
Preferably, described step 1) calcined temperature in is 1000 ℃～1300 ℃, and the pre-burning time is 2～4 hours.
Preferably, described step 1) and step 2) in ball-milling medium all be selected from dehydrated alcohol or deionized water, Ball-milling Time is 20～24 hours.
Preferably, described step 1) and step 2) in mechanical milling process in, the mass ratio of zirconia ball and ball milling material is 1.2～1.5: 1; The mass ratio of ball-milling medium and ball milling material is 1.5～3.0: 1.
Described ball milling material refers to the raw material of ball milling, in step 1) in the raw material of ball milling be by A, BaCO
3, SrCO
3, TiO
2And WO
3The mixing raw material of phosphor composing, step 2) raw material of ball milling is the mixed powder of pre-burning in.
Preferably, the binding agent described step 3) is that mass percent is 8%～10% polyvinyl alcohol water solution.
Preferably, described step 4) the sticking temperature of processing of the row in is 550 ℃～600 ℃, and row is 4～10h in the sticking treatment time.
Preferably, described step 4) sintering temperature in is 1200 ℃～1500 ℃, and sintering time is 2～4 hours.
The present invention adopts traditional electronic ceramic technology, adopt the transition metal element compound quality to compare doping vario-property, development obtains can be used for high Q value, the low-k of adjustable microwave device, the transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material of the adjustable rate of high dielectric, and the adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material of dielectric of the present invention has following principal feature:
(1) Curie temperature of this stupalith system can be with Ba/Sr and x%A+[(1-x%) * y%] Ba
1-zSr
zTiO
3+ [(1-x%) * (1-y%)] BaWO
4(A=V
2O
5, Cr
2O
3, MnCO
3, Co
2O
3Or NiF
20＜x＜5; Y=5～95; Z=0.4～0.6) mass ratio is adjustable continuously in very wide scope, can require to adjust according to the working temperature of designed adjustable microwave device structure and the performance of material system;
(2) by Ba/Sr and x%A+[(1-x%) * y%] Ba
1-zSr
zTiO
3+ [(1-x%) * (1-y%)] BaWO
4(A is V
2O
5, Cr
2O
3, MnCO
3, Co
2O
3Or NiF
20＜x＜5; Y=5～95; Z=0.4～0.6) variation of component ratio, the specific inductivity of ceramic medium material can be adjustable continuously, can obtain the material system of specific inductivity seriation, widened the range of application of material;
(3) have high Q value (low-dielectric loss), low specific inductivity and the high adjustable rate of dielectric (such as 0.2%Co
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4Middle Q value can be up to 292, specific inductivity is 92, adjustable rate is 20%), and specific inductivity seriation (that is: specific inductivity can be regulated the mass percent of component and the controllability that recently reaches specific inductivity with variation adjusting Ba, the Sr of z value by the numerical value that changes x, y).
(4) its composition is with a cube Ba
1-zSr
zTiO
3Phase and cubic BaWO
4Mutually coexistence has excellent micro-wave dielectric over-all properties;
(5) excellent comprehensive microwave dielectric property is, specific inductivity is about 100, and the adjustable rate of dielectric is more than 15%, and the Q value is more than 150;
(6) adopt traditional electronic ceramic technology, technique is simple, and cost is low, the side effect of material system environment-protecting asepsis, and excellent performance is applicable to the material of the adjustable microwave components and parts such as electronic tuning microwave resonator, wave filter and microwave-medium antenna.
Description of drawings
Fig. 1 is 0.2%Co
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The X-ray diffraction analysis collection of illustrative plates of adjustable microwave doped ceramics dielectric material.
Fig. 2 is 0.2%Co
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of adjustable microwave doped ceramics dielectric material and the relation curve of dielectric loss and temperature.
Fig. 3 is 0.2%Co
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of adjustable microwave doped ceramics dielectric material and the relation curve of strength of electric field.
Fig. 4 is 0.2%MnCO
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The X-ray diffraction analysis collection of illustrative plates of adjustable microwave doped ceramics dielectric material.
Fig. 5 is 0.2%MnCO
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of adjustable microwave doped ceramics dielectric material and the relation curve of dielectric loss and temperature.
Fig. 6 is 0.2%MnCO
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of adjustable microwave doped ceramics dielectric material and the relation curve of strength of electric field.
Fig. 7 is 0.2%V
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The X-ray diffraction analysis collection of illustrative plates of adjustable microwave doped ceramics dielectric material.
Fig. 8 is 0.2%V
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of adjustable microwave doped ceramics dielectric material and the relation curve of dielectric loss and temperature.
Fig. 9 is 0.2%V
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of adjustable microwave doped ceramics dielectric material and the relation curve of strength of electric field.
Figure 10 is 0.2%NiF
2+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The X-ray diffraction analysis collection of illustrative plates of adjustable microwave doped ceramics dielectric material.
Figure 11 is 0.2%NiF
2+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of adjustable microwave doped ceramics dielectric material and the relation curve of dielectric loss and temperature.
Figure 12 is 0.2%NiF
2+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of adjustable microwave doped ceramics dielectric material and the relation curve of strength of electric field.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used for explanation the present invention and are not used in restriction protection scope of the present invention.
Embodiment 1 preparation low-k, high Q value, the 0.2%Co that dielectric is adjustable
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The doped ceramics dielectric material
Respectively according to 0.2%Co
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2And Co
2O
3, WO
3Raw material (as shown in table 1).
Raw material sources: BaCO
3(99.8%, Alfa Aesar China LTD.), SrCO
3(99.0%, Alfa Aesar ChinaLTD.), TiO
2(99.9%, Alfa Aesar China LTD.) and Co
2O
3(99.99%, Chemical Reagent Co., Ltd., Sinopharm Group), WO
3(99.8%, Alfa Aesar China LTD.)
Table 1.0.2%Co
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The proportioning raw materials of doped ceramics dielectric material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | Co 2O 3 | WO 3 |
| Quality/g | 14.790 | 5.358 | 5.745 | 0.060 | 9.029 |
Above-mentioned powder is placed nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water, ball milling 24 hours, the discharging oven dry is rear 1000 ℃ of pre-burnings 4 hours, powder after the grinding places nylon ball grinder, add zirconia ball (mass ratio of zirconia ball and ball milling material is 1.2: 1) and deionized water (mass ratio of deionized water and ball milling material is 3.0: 1), ball milling 24 hours, powder is crossed 200 mesh sieves after the discharging oven dry; According to traditional electronic ceramic technology, the polyvinyl alcohol (PVA) of employing 8% carries out granulation as binding agent, and under 10MPa pressure, dry method is pressed into diameter
The right cylinder of green sheet and 10mm * 5mm, 12mm * 6mm, 15mm * 7mm, 18mm * 8mm, after 550 ℃ of sticking processing of row, sample is under air atmosphere, and sintering temperature is 1300 ℃, is incubated after 4 hours, obtains 0.2%Co
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4Ceramics sample.The ceramics sample that makes is carried out first phase and microstructure analysis, then to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing, its relevant dielectric properties see Table 2.
Table 2.0.2%Co
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The relevant dielectric properties of dielectric adjustable microwave doped ceramics dielectric material
In the present embodiment, 0.2%Co
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The X-ray diffraction analysis collection of illustrative plates of dielectric adjustable microwave doped ceramics dielectric material as shown in Figure 1.Result among Fig. 1 shows: its composition is with a cube Ba
0.5Sr
0.5TiO
3Phase and cubic BaWO
4The phase structure coexistence.
In the present embodiment, 0.2%Co
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of dielectric adjustable microwave doped ceramics dielectric material and the relation curve of loss and temperature as shown in Figure 2, the result among Fig. 2 shows that the Curie peak of stoichiometric ratio doped and compounded pottery moves along with the increase generation disperse of doping and to the low temperature direction.
In the present embodiment, 0.2%Co
2O
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of dielectric adjustable microwave doped ceramics dielectric material and the relation curve of strength of electric field as shown in Figure 3, the test result among Fig. 3 shows that the doped and compounded pottery has higher dielectric adjustable, up to 20%.Obtain comparatively desirable comprehensive microwave property after the doped and compounded, as shown in table 2.
Respectively according to 0.2%MnCO
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2And Co
2O
3, WO
3Raw material (as shown in table 3).
Raw material sources: BaCO
3(99.8%, Alfa Aesar China LTD.), SrCO
3(99.0%, Alfa Aesar ChinaLTD.), TiO
2(99.9%, Alfa Aesar China LTD.) and MnCO
3(99.99%, Chemical Reagent Co., Ltd., Sinopharm Group), WO
3(99.8%, Alfa Aesar China LTD.)
Table 3.0.2%MnCO
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The proportioning raw materials of doped ceramics dielectric material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | MnCO 3 | WO 3 |
| Quality/g | 14.790 | 5.358 | 5.745 | 0.060 | 9.029 |
Above-mentioned powder is placed nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water, ball milling 24 hours, the discharging oven dry is rear 1000 ℃ of pre-burnings 4 hours, powder after the grinding places nylon ball grinder, add zirconia ball (mass ratio of zirconia ball and ball milling material is 1.2: 1) and deionized water (mass ratio of deionized water and ball milling material is 3.0: 1), ball milling 24 hours, powder is crossed 200 mesh sieves after the discharging oven dry; According to traditional electronic ceramic technology, the polyvinyl alcohol (PVA) of employing 8% carries out granulation as binding agent, and under 10MPa pressure, dry method is pressed into diameter
The right cylinder of green sheet and 10mm * 5mm, 12mm * 6mm, 15mm * 7mm, 18mm * 8mm, after 550 ℃ of sticking processing of row, sample is under air atmosphere, and sintering temperature is 1300 ℃, is incubated after 4 hours, obtains 0.2%MnCO
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4Ceramics sample.The ceramics sample that makes is carried out first phase and microstructure analysis, then to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing, its relevant dielectric properties see Table 4.
Table 4.0.2%MnCO
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The relevant dielectric properties of dielectric adjustable microwave doped ceramics dielectric material
In the present embodiment, 0.2%MnCO
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The X-ray diffraction analysis collection of illustrative plates of dielectric adjustable microwave doped ceramics dielectric material as shown in Figure 4.Result among Fig. 4 shows: its composition is with a cube Ba
0.5Sr
0.5TiO
3Phase and cubic BaWO
4The phase structure coexistence.
In the present embodiment, 0.2%MnCO
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of dielectric adjustable microwave doped ceramics dielectric material and the relation curve of loss and temperature as shown in Figure 5, the result among Fig. 5 shows that the Curie peak of stoichiometric ratio composite ceramics moves along with the increase generation disperse of doping and to the low temperature direction.
In the present embodiment, 0.2%MnCO
3+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of dielectric adjustable microwave doped ceramics dielectric material and the relation curve of strength of electric field as shown in Figure 6, the test result among Fig. 6 shows that the doped and compounded pottery has higher dielectric adjustable, is 24%.Obtain comparatively desirable comprehensive microwave property after the doped and compounded, as shown in table 4.
Embodiment 3 preparation low-ks, high Q value, the 0.2%V that dielectric is adjustable
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The doped ceramics dielectric material
Respectively according to 0.2%V
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2And Co
2O
3, WO
3Raw material (as shown in table 5).
Raw material sources: BaCO
3(99.8%, Alfa Aesar China LTD.), SrCO
3(99.0%, Alfa Aesar ChinaLTD.), TiO
2(99.9%, Alfa Aesar China LTD.) and V
2O
5(99.99%, Chemical Reagent Co., Ltd., Sinopharm Group), WO
3(99.8%, Alfa Aesar China LTD.)
Table 5.0.2%V
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The proportioning raw materials of doped ceramics dielectric material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | V 2O 5 | WO 3 |
| Quality/g | 14.790 | 5.358 | 5.745 | 0.060 | 9.029 |
Above-mentioned powder is placed nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water, ball milling 24 hours, the discharging oven dry is rear 1000 ℃ of pre-burnings 4 hours, powder after the grinding places nylon ball grinder, add zirconia ball (mass ratio of zirconia ball and ball milling material is 1.2: 1) and deionized water (mass ratio of deionized water and ball milling material is 3.0: 1), ball milling 24 hours, powder is crossed 200 mesh sieves after the discharging oven dry; According to traditional electronic ceramic technology, the polyvinyl alcohol (PVA) of employing 8% carries out granulation as binding agent, and under 10MPa pressure, dry method is pressed into diameter
The right cylinder of green sheet and 10mm * 5mm, 12mm * 6mm, 15mm * 7mm, 18mm * 8mm, after 550 ℃ of sticking processing of row, sample is under air atmosphere, and sintering temperature is 1300 ℃, is incubated after 4 hours, obtains 0.2%V
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4Ceramics sample.The ceramics sample that makes is carried out first phase and microstructure analysis, then to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing, its relevant dielectric properties see Table 6.
Table 6.0.2%V
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The relevant dielectric properties of dielectric adjustable microwave doped ceramics dielectric material
In the present embodiment, 0.2%V
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The X-ray diffraction analysis collection of illustrative plates of dielectric adjustable microwave doped ceramics dielectric material as shown in Figure 7.Result among Fig. 7 shows: its composition is with a cube Ba
0.5Sr
0.5TiO
3Phase and cubic BaWO
4The phase structure coexistence.
In the present embodiment, 0.2%V
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of dielectric adjustable microwave doped ceramics dielectric material and the relation curve of loss and temperature as shown in Figure 8, the result among Fig. 8 shows that the Curie peak of stoichiometric ratio composite ceramics moves along with the increase generation disperse of doping and to the low temperature direction.
In the present embodiment, 0.2%V
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of dielectric adjustable microwave doped ceramics dielectric material and the relation curve of strength of electric field as shown in Figure 9, the test result among Fig. 9 shows that the doped and compounded pottery has higher dielectric adjustable, is 23%.Obtain comparatively desirable microwave property after the doped and compounded, as shown in table 6.
Embodiment 4 preparation low-ks, high Q value, the 0.2%NiF that dielectric is adjustable
2+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The doped ceramics dielectric material
Respectively according to 0.2%NiF
2+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2And Co
2O
3, WO
3Raw material (as shown in table 7).
Raw material sources: BaCO
3(99.8%, Alfa Aesar China LTD.), SrCO
3(99.0%, Alfa Aesar ChinaLTD.), TiO
2(99.9%, Alfa Aesar China LTD.) and NiF
2(99.99%, Chemical Reagent Co., Ltd., Sinopharm Group), WO
3(99.8%, Alfa Aesar China LTD.)
Table 7.0.2%V
2O
5+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The proportioning raw materials of doped ceramics dielectric material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | NiF 2 | WO 3 |
| Quality/g | 14.790 | 5.358 | 5.745 | 0.060 | 9.029 |
Above-mentioned powder is placed nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water, ball milling 24 hours, the discharging oven dry is rear 1000 ℃ of pre-burnings 4 hours, powder after the grinding places nylon ball grinder, add zirconia ball (mass ratio of zirconia ball and ball milling material is 1.2: 1) and deionized water (mass ratio of deionized water and ball milling material is 3.0: 1), ball milling 24 hours, powder is crossed 200 mesh sieves after the discharging oven dry; According to traditional electronic ceramic technology, the polyvinyl alcohol (PVA) of employing 8% carries out granulation as binding agent, and under 10MPa pressure, dry method is pressed into diameter
The right cylinder of green sheet and 10mm * 5mm, 12mm * 6mm, 15mm * 7mm, 18mm * 8mm, after 550 ℃ of sticking processing of row, sample is under air atmosphere, and sintering temperature is 1300 ℃, is incubated after 4 hours, obtains 0.2%NiF
2+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4Ceramics sample.The ceramics sample that makes is carried out first phase and microstructure analysis, then to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing, its relevant dielectric properties see Table 8.
Table 8.0.2%NiF
2+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The relevant dielectric properties of dielectric adjustable microwave doped ceramics dielectric material
In the present embodiment, 0.2%NiF
2+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The X-ray diffraction analysis collection of illustrative plates of dielectric adjustable microwave doped ceramics dielectric material as shown in figure 10.Result among Figure 10 shows: its composition is with a cube Ba
0.5Sr
0.5TiO
3Phase and cubic BaWO
4The phase structure coexistence.
In the present embodiment, 0.2%NiF
2+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of dielectric adjustable microwave doped ceramics dielectric material and the relation curve of loss and temperature as shown in figure 11, the result among Figure 11 shows that the Curie peak of stoichiometric ratio composite ceramics moves along with the increase generation disperse of doping and to the low temperature direction.
In the present embodiment, 0.2%NiF
2+ 49.9%Ba
0.5Sr
0.5TiO
3+ 49.9%BaWO
4The specific inductivity of dielectric adjustable microwave doped ceramics dielectric material and the relation curve of strength of electric field as shown in figure 12, the test result among Figure 12 shows that the doped and compounded pottery has higher dielectric adjustable, is 25%.Obtain comparatively desirable microwave property after the doped and compounded, as shown in table 8.
Respectively according to 0.1%MnCO
3+ 49.95%Ba
0.4Sr
0.6TiO
3+ 49.95%BaWO
4Mole metering ratio, take by weighing BaCO
3, SrCO
3, TiO
2And MnCO
3, WO
3Raw material (as shown in table 9).
Raw material sources: BaCO
3(99.8%, Alfa Aesar China LTD.), SrCO
3(99.0%, Alfa Aesar ChinaLTD.), TiO
2(99.9%, the high-new inorganic materials in Foshan company limited) and MnCO
3(99.9%, Alfa Aesar China LTD.), WO
3(99.8%, Alfa Aesar China LTD.)
Table 9.0.1%MnCO
3+ 49.95%Ba
0.4Sr
0.6TiO
3+ 49.95%BaWO
4The proportioning raw materials of doped ceramics dielectric material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | MnCO 3 | WO 3 |
| Quality/g | 14.865 | 6.593 | 5.891 | 0.030 | 9.038 |
Above-mentioned powder is placed nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water, ball milling 24 hours, the discharging oven dry is rear 1100 ℃～1300 ℃ pre-burnings 4 hours, powder after the grinding places nylon ball grinder, add zirconia ball (mass ratio of zirconia ball and ball milling material is 1.5: 1) and dehydrated alcohol (mass ratio of dehydrated alcohol and ball milling material is 1.5: 1), ball milling 24 hours, powder is crossed 200 mesh sieves after the discharging oven dry; According to traditional electronic ceramic technology, the polyvinyl alcohol (PVA) of employing 10% carries out granulation as binding agent, and under 100MPa pressure, dry method is pressed into diameter
The right cylinder of green sheet and 10mm * 5mm, 12mm * 6mm, 15mm * 7mm, 18mm * 8mm, after 600 ℃ of sticking processing of row, sample is under air atmosphere, and sintering temperature is 1500 ℃, is incubated after 2 hours, obtains 0.1%MnCO
3+ 49.95%Ba
0.4Sr
0.6TiO
3+ 49.95%BaWO
4Ceramics sample.The ceramics sample that makes is carried out first phase and microstructure analysis, then to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing, its relevant dielectric properties see Table 10.After tested, the doped ceramics dielectric material that makes in the present embodiment has high Q value, low specific inductivity, the high characteristics such as adjustable rate.
Table 10.0.1%MnCO
3+ 49.95%Ba
0.4Sr
0.6TiO
3+ 49.95%BaWO
4The relevant dielectric properties of dielectric adjustable microwave doped ceramics dielectric material
Embodiment 6 preparation low-ks, high Q value, the 4%NiF that dielectric is adjustable
2+ 38.4%Ba
0.6Sr
0.4TiO
3+ 57.6%BaWO
4The doped ceramics dielectric material
Respectively according to 4%NiF
2+ 38.4%Ba
0.6Sr
0.4TiO
3+ 57.6%BaWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2And NiF
2, WO
3Raw material (as shown in table 11).
Raw material sources: BaCO
3(99.8%, Alfa Aesar China LTD.), SrCO
3(99.0%, Alfa Aesar ChinaLTD.), TiO
2(99.9%, the high-new inorganic materials in Foshan company limited) and MnCO
3(99.9%, Alfa Aesar China LTD.), WO
3(99.8%, Alfa Aesar China LTD.)
Table 11.4%NiF
2+ 38.4%Ba
0.6Sr
0.4TiO
3+ 57.6%BaWO
4The proportioning raw materials of doped ceramics dielectric material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | NiF 2 | WO 3 |
| Quality/g | 15.278 | 3.221 | 4.318 | 1.201 | 10.422 |
Above-mentioned powder is placed nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water, ball milling 24 hours, the discharging oven dry is rear 1000 ℃～1200 ℃ pre-burnings 4 hours, powder after the grinding places nylon ball grinder, add zirconia ball (mass ratio of zirconia ball and ball milling material is 1.2: 1) and deionized water (mass ratio of deionized water and ball milling material is 3.0:1), ball milling 24 hours, powder is crossed 200 mesh sieves after the discharging oven dry; According to traditional electronic ceramic technology, the polyvinyl alcohol (PVA) of employing 8% carries out granulation as binding agent, and under 10MPa pressure, dry method is pressed into diameter
The right cylinder of green sheet and 10mm * 5mm, 12mm * 6mm, 15mm * 7mm, 18mm * 8mm, after 550 ℃ of sticking processing of row, sample is under air atmosphere, and sintering temperature is 1350 ℃, is incubated after 4 hours, obtains 4%NiF
2+ 38.4%Ba
0.6Sr
0.4TiO
3+ 57.6%BaWO
4Ceramics sample.The ceramics sample that makes is carried out first phase and microstructure analysis, then to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing, its relevant dielectric properties see Table 12.After tested, the doped ceramics dielectric material that makes in the present embodiment has high Q value, low specific inductivity, the higher characteristics such as adjustable rate.
Table 12.4%NiF
2+ 38.4%Ba
0.6Sr
0.4TiO
3+ 57.6%BaWO
4The relevant dielectric properties of dielectric adjustable microwave doped ceramics dielectric material
Embodiment 7 preparation low-ks, high Q value, the 1%V that dielectric is adjustable
2O
5+ 14.85%Ba
0.5Sr
0.5TiO
3+ 84.15%BaWO
4The doped ceramics dielectric material
Respectively according to 1%V
2O
5+ 14.85%Ba
0.5Sr
0.5TiO
3+ 84.15%BaWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2And V
2O
5, WO
3Raw material (as shown in table 13).
Raw material sources: BaCO
3(99.8%, Alfa Aesar China LTD.), SrCO
3(99.0%, Alfa Aesar ChinaLTD.), TiO
2(99.9%, the high-new inorganic materials in Foshan company limited) and V
2O
5(99.9%, Alfa Aesar China LTD.), WO
3(99.8%, Alfa Aesar China LTD.)
Table 13.1%V
2O
5+ 14.85%Ba
0.5Sr
0.5TiO
3+ 84.15%BaWO
4The proportioning raw materials of doped ceramics dielectric material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | V 2O 5 | WO 3 |
| Quality/g | 15.074 | 1.594 | 1.710 | 0.300 | 15.226 |
Above-mentioned powder is placed nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water, ball milling 24 hours, the discharging oven dry is rear 1000 ℃～1200 ℃ pre-burnings 4 hours, powder after the grinding places nylon ball grinder, add zirconia ball (mass ratio of zirconia ball and ball milling material is 1.2: 1) and deionized water (mass ratio of deionized water and ball milling material is 3.0: 1), ball milling 20 hours, powder is crossed 200 mesh sieves after the discharging oven dry; According to traditional electronic ceramic technology, the polyvinyl alcohol (PVA) of employing 8% carries out granulation as binding agent, and under 10MPa pressure, dry method is pressed into diameter
The right cylinder of green sheet and 10mm * 5mm, 12mm * 6mm, 15mm * 7mm, 18mm * 8mm, after 550 ℃ of sticking processing of row, sample is under air atmosphere, and sintering temperature is 1350 ℃, is incubated after 4 hours, obtains 1%V
2O
5+ 14.85%Ba
0.5Sr
0.5TiO
3+ 84.15%BaWO
4Ceramics sample.The ceramics sample that makes is carried out first phase and microstructure analysis, then to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing, its relevant dielectric properties see Table 14.After tested, the doped ceramics dielectric material that makes in the present embodiment has high Q value, low specific inductivity, the high characteristics such as adjustable rate.
Table 14.1%V
2O
5+ 14.85%Ba
0.5Sr
0.5TiO
3+ 84.15%BaWO
4The relevant dielectric properties of dielectric adjustable microwave doped ceramics dielectric material
Respectively according to 2%Cr
2O
3+ 88.2%Ba
0.6Sr
0.4TiO
3+ 9.8%BaWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2And Cr
2O
3, WO
3Raw material (as shown in Table 15).
Raw material sources: BaCO
3(99.8%, Alfa Aesar China LTD.), SrCO
3(99.0%, Alfa Aesar ChinaLTD.), TiO
2(99.9%, the high-new inorganic materials in Foshan company limited) and Cr
2O
3(99.99%, Alfa Aesar China LTD.), WO
3(99.8%, Alfa Aesar China LTD.)
Table 15.2%Cr
2O
3+ 88.2%Ba
0.6Sr
0.4TiO
3+ 9.8%BaWO
4The proportioning raw materials of doped ceramics dielectric material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | Cr 2O 3 | WO 3 |
| Quality/g | 16.226 | 7.399 | 9.917 | 0.601 | 1.773 |
Above-mentioned powder is placed nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water, ball milling 24 hours, the discharging oven dry is rear 1000 ℃ of pre-burnings 4 hours, powder after the grinding places nylon ball grinder, add zirconia ball (mass ratio of zirconia ball and ball milling material is 1.2: 1) and deionized water (mass ratio of deionized water and ball milling material is 3.0: 1), ball milling 24 hours, powder is crossed 200 mesh sieves after the discharging oven dry; According to traditional electronic ceramic technology, the polyvinyl alcohol (PVA) of employing 8% carries out granulation as binding agent, and under 10MPa pressure, dry method is pressed into diameter
The right cylinder of green sheet and 10mm * 5mm, 12mm * 6mm, 15mm * 7mm, 18mm * 8mm, after 550 ℃ of sticking processing of row, sample is under air atmosphere, and sintering temperature is 1200～1300 ℃, is incubated after 4 hours, obtains 2%Cr
2O
3+ 88.2%Ba
0.6Sr
0.4TiO
3+ 9.8%BaWO
4Ceramics sample.The ceramics sample that makes is carried out first phase and microstructure analysis, then to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing, its relevant dielectric properties see Table 16.After tested, the doped ceramics dielectric material that makes in the present embodiment has high Q value, low specific inductivity, the higher characteristics such as adjustable rate.
Table 16.2%Cr
2O
3+ 88.2%Ba
0.6Sr
0.4TiO
3+ 9.8%BaWO
4The relevant dielectric properties of dielectric adjustable microwave doped ceramics dielectric material
Claims (9)
1. transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material that dielectric is adjustable, its component and weight percentage are:
A x％
Ba
1-zSr
zTiO
3 (1-x％)*y％
BaWO
4 (1-x％)*(1-y％)
Wherein, described A is selected from V
2O
5, Cr
2O
3, MnCO
3, Co
2O
3Or NiF
2
X% is weight percentage, and span is 0.05wt%≤x%≤4wt%;
Y% is weight percentage, and span is 35wt%≤y%≤65wt%;
The span of z is 0.4≤z≤0.6.
2. the adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material of dielectric as claimed in claim 1 is characterized in that, the span of described x% is 0.05wt%≤x%≤1wt%.
3. the adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material preparation method of dielectric as claimed in claim 1 or 2 comprises the steps:
1) selects A powder, BaCO
3Powder, SrCO
3Powder, TiO
2Powder and WO
3Powder is as main raw material, according to x%A+[(1-x%) * y%] Ba
1-zSr
zTiO
3+ [(1-x%) * (1-y%)] BaWO
4In the molar ratio ingredient of various elements, add zirconia ball and ball-milling medium in the mixing raw material for preparing, after ball milling and the discharging oven dry, obtain mixed powder through pre-burning and grinding again;
2) in step 1) in add zirconia ball and ball-milling medium in the mixed powder that makes, sieve after ball milling and the discharging oven dry;
3) adopt binding agent to step 2) in powder after sieving carry out granulation, then be pressed into the ceramic green sheet;
4) with step 3) in the ceramic green sheet that makes carry out sintering through row is sticking after processing, obtain described transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material.
4. the adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material preparation method of dielectric as claimed in claim 3, it is characterized in that, described step 1) calcined temperature in is 1000 ℃～1300 ℃, and the pre-burning time is 2～4h.
5. the adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material preparation method of dielectric as claimed in claim 3, it is characterized in that, described step 1) and step 2) in ball-milling medium all be selected from dehydrated alcohol or deionized water, Ball-milling Time is 20～24h.
6. the adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material preparation method of dielectric as claimed in claim 3, it is characterized in that described step 3) in binding agent be that mass percent is 8%～10% polyvinyl alcohol water solution.
7. the adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material preparation method of dielectric as claimed in claim 3, it is characterized in that, described step 4) the sticking temperature of processing of the row in is 550 ℃～600 ℃, and row is 4～10h the sticking time of processing.
8. the adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material preparation method of dielectric as claimed in claim 3, it is characterized in that, described step 4) sintering temperature in is 1200 ℃～1500 ℃, and sintering time is 2～4h.
9. the adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material of dielectric as claimed in claim 1 or 2 is for the preparation of the adjustable microwave components and parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010206295 CN101891463B (en) | 2010-06-22 | 2010-06-22 | Dielectric adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010206295 CN101891463B (en) | 2010-06-22 | 2010-06-22 | Dielectric adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101891463A CN101891463A (en) | 2010-11-24 |
| CN101891463B true CN101891463B (en) | 2013-02-13 |
Family
ID=43100842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010206295 Expired - Fee Related CN101891463B (en) | 2010-06-22 | 2010-06-22 | Dielectric adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101891463B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515721B (en) * | 2011-11-25 | 2014-05-21 | 山东同方鲁颖电子有限公司 | Low-dielectric-constant microwave medium ceramic and preparation method thereof |
| CN110483035B (en) * | 2019-09-24 | 2022-04-15 | 福建省德化县华瓷新材料科技有限公司 | Microwave dielectric ceramic material, preparation method and application thereof, and filter ceramic material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541187A (en) * | 2001-01-10 | 2004-10-27 | ���Ͽع�����˾ | Coated barium titanatep based particles and process for prodn. thereof |
| CN101665353A (en) * | 2009-09-08 | 2010-03-10 | 同济大学 | Dielectric tunable barium-strontium titanate-based composite tungstate microwave dielectric material and preparation thereof |
-
2010
- 2010-06-22 CN CN 201010206295 patent/CN101891463B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541187A (en) * | 2001-01-10 | 2004-10-27 | ���Ͽع�����˾ | Coated barium titanatep based particles and process for prodn. thereof |
| CN101665353A (en) * | 2009-09-08 | 2010-03-10 | 同济大学 | Dielectric tunable barium-strontium titanate-based composite tungstate microwave dielectric material and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 宋佳等.MnCO3对BMT系陶瓷结构和微波特性的影响.《压电与声光》.2004,第26卷(第6期),第488-490页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101891463A (en) | 2010-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101007736A (en) | Ba1-xSrxTiO3-Mg2TiO4 two-phase composite ceramic material and its preparing process | |
| CN101955356B (en) | Tunable dielectric barium strontium titanate based composite silicate microwave dielectric material and preparation thereof | |
| CN108046795B (en) | High-dielectric adjustable barium strontium titanate-based composite aluminosilicate ceramic dielectric material | |
| CN101172850B (en) | Multiple phase ceramic material with adjustable dielectric | |
| CN101665353B (en) | Dielectric tunable barium-strontium titanate-based composite tungstate microwave dielectric material and preparation thereof | |
| CN105693235B (en) | High dielectric microwave medium ceramic material and preparation method thereof | |
| CN101486571B (en) | High Q electricity adjustable Ba1-xSrxTi1-yMnyO3 ceramic dielectric material and preparation thereof | |
| CN101891463B (en) | Dielectric adjustable transition metal element compound doped barium-strontium titanate compound-barium tungstate ceramic-dielectric material and preparation method thereof | |
| CN103435349B (en) | Method for preparing high-quality-factor neodymium niobate dielectric ceramic by means of manganese ion substitution | |
| CN109467432A (en) | A kind of Mg-Ti-Ta base microwave medium ceramic material and preparation method thereof | |
| CN102515746A (en) | Microwave dielectrically-adjustable material of barium strontium titanate composite molybdate and preparation method for same | |
| CN100480212C (en) | Ba1-XSrXTiO3-BaX6Ti6O19(X=Mg, zn) two-phase composite microwave ceramic material and its preparation method | |
| CN101492294B (en) | Dielectric adjustable microwave ceramic dielectric material and method of producing the same | |
| CN101723662A (en) | Dielectric adjustable BST-MB two-phase compound microwave ceramic material and method for preparing same | |
| CN101575208B (en) | Low-temperature sintered and low-loss BaO-CeO2-TiO2 series microwave dielectric ceramic | |
| CN101007737A (en) | Rare earth oxide doped and modified barium zirconate titanate dielectric adjustable ceramic material and its preparation method | |
| CN105060888A (en) | Low-loss stable niobic acid neodymium ceramic prepared through aluminum oxide doping | |
| CN102633500B (en) | Dielectric-adjustable low-temperature co-firing ceramic material and preparation method thereof | |
| CN110386815B (en) | Barium strontium titanate composite zinc aluminate ceramic material with high adjustable rate, low loss and practicability | |
| CN110386816B (en) | Barium strontium titanate composite zinc gallate ceramic material with high adjustable rate and low loss | |
| CN101265085B (en) | Dielectric adjustable Ba[1-x]SrxTiO3-MgAl2O4 diphase composite microwave ceramic material and preparation method thereof | |
| CN111548158B (en) | Ultralow temperature sintering microwave medium composite material Sr1-xCaxV2O6And method for preparing the same | |
| CN102358930B (en) | Low-loss high-dielectric adjustable titanic acid strontium barium substrate ceramic material and preparation method thereof | |
| CN106866143A (en) | Microwave complex phase ceramic AWO4 TiO2 and preparation method thereof | |
| CN103964841B (en) | A kind of microwave-tuned composite ceramic material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130213 Termination date: 20150622 |
|
| EXPY | Termination of patent right or utility model |