CN101665353B - Dielectric tunable barium-strontium titanate-based composite tungstate microwave dielectric material and preparation thereof - Google Patents
Dielectric tunable barium-strontium titanate-based composite tungstate microwave dielectric material and preparation thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electronic materials and parts, particularly relates to a dielectric tunable barium-strontium titanate-based composite tungstate ceramic dielectric material and preparation thereof. The components of the dielectric tunable barium-strontium titanate-based composite tungstate ceramic dielectric material are as follows: (1-x%)Ba(1-y)SryTiO3 plus x%AWO4, wherein A is selected from Ba, Ca, Mg or Zn; the value range of x is that x% is more than 0wt% and less than 100wt%; and the value range of y is more than or equal to 0.4 and less than or equal to 0.6. The dielectric tunable barium-strontium titanate-based composite tungstate ceramic dielectric material has high Q value, low dielectric constant and a certain dielectric turnable ratio, and can be broadly used for preparing tunable microwave devices such as electric tuning microwave resonators, filters, mirowave polyrod antennas and the like.
Description
Technical field
The invention belongs to electronic material and device technology field, be specifically related to adjustable barium-strontium titanate-based composite tungstate microwave dielectric material of a kind of dielectric and preparation thereof.
Background technology
Have high-k, low-dielectric loss, nonlinear dielectric constant is adjustable with and the adjustable calcium titanium ore structure strontium-barium titanate ferroelectric material of Curie temperature aspect microwave adjustable device (like shifter, wave filter, VC and retarding line etc.) obtain increasingly extensive concern, especially at the focus of research at present especially aspect microwave phase shifter.But the BST stupalith with high-k is difficult to satisfy itself and driving source internal driving coupling and high-power requirement, this big limitations its application in the microwave adjustable device field.The Q value is to weigh the significant parameter of inductance component, and the Q value is meant when inducer is worked under the voltage of alternating current of a certain frequency, the ratio of the induction reactance that is appeared loss resistance equivalent with it.The Q value of inducer is high more, and its loss is more little, and efficient is high more.The specific inductivity of strontium-barium titanate BST material changes with the variation of applying direct current electric field, when voltage when V (0) changes to V (app), 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, promptly use Tunability (being abbreviated as T)=[ε
R (0)-ε
R (app)]/ε
R (0)* 100% representes.And will produce corresponding differential phase shift when applying the light (microwave) of a particular frequencies simultaneously, reach the purpose that changes phase place.Material with this specific character becomes electrooptical material.The ability that shifter changes the phasing degree is mainly decided by adjustability, so high adjustability is very important for the shifter material.
Therefore, how to prepare both had low-k, high Q value, the material system that has certain dielectric tunable characteristic again is technological difficulties.
Ceramic Composite all is that the electron ceramic material modification is used always and one of the most effective means the most all the time; Material through the different mass ratio is compound; To get in the crystalline network of crystalline material with different modes in various degree; Cause the change of material microstructure, thereby adjust and improve the correlated performance of material effectively.In the prior art, there is the researchist to adopt MgO, MgAl
2O
6Deng more compound than strontium-barium titanate with different mass, development obtains having low-k, high Q value and the ceramic medium material system of dielectric tunable characteristic necessarily.People such as the Peng Liu of Shaanxi Normal University have carried out systematic research to the difference amount than strontium-barium titanate composite titanic acid magnesium, obtain microwave ceramic dielectric material (ε
r=76.5, δ=0.0007～10kHz, T=10.2).Yet relevant report is not seen in the micro-wave dielectric tunable characteristic research of strontium-barium titanate composite tungstate material as yet.
Summary of the invention
The purpose of this invention is to provide a kind of dielectric adjustable barium-strontium titanate-based composite tungstate ceramic medium material and preparation thereof, the barium-strontium titanate-based composite tungstate ceramic medium material that this dielectric is adjustable has high Q value and the adjustable characteristic of dielectric.
The component of the barium-strontium titanate-based composite tungstate ceramic medium material that dielectric of the present invention is adjustable is: (1-x%) Ba
1-ySr
yTiO
3+ x%AWO
4Wherein, A is selected from Ba, Ca, Mg or Zn, and x% is weight percentage, and span is 0wt%＜x%＜100wt%, and the span of y is 0.4≤y≤0.6.
Preferable, the span of said x% is 5wt%≤x%≤50wt%, further is preferably 20wt%≤x%≤40wt%.
Preferred, the general formula of the component of the barium-strontium titanate-based composite tungstate ceramic medium material that said dielectric is adjustable is: 65%Ba
0.5Sr
0.5TiO
3+ 35%AWO
4, wherein, A is selected from Mg, Zn, Ba or Ca.
In the component general formula of the barium-strontium titanate-based composite tungstate ceramic medium material that said dielectric is adjustable, 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 said barium-strontium titanate-based composite tungstate ceramic medium material, said AWO
4Mass percent; (1-x%) representative is in the total mass of said barium-strontium titanate-based composite tungstate ceramic medium material, said Ba
1-ySr
yTiO
3Mass percent.
The preparation method of the barium-strontium titanate-based composite tungstate ceramic medium material 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 for use to contain A element material powder, SrCO
3Powder, TiO
2Powder and WO
3Powder is as main raw material, according to (1-x%) Ba
1-ySr
yTiO
3+ x%AWO
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) add zirconia ball and ball-milling medium in the mixed powder that in step 1), makes, sieve after ball milling and the discharging oven dry;
3) adopt sticker to step 2) in powder after sieving carry out granulation, at 10MPa～100MPa pressure pressed molding ceramic green sheet;
4) the ceramic green sheet that makes in the step 3) is carried out sintering after arranging sticking the processing, can obtain said barium-strontium titanate-based composite tungstate ceramic medium material.
The A element raw material that contains in the said step 1) is selected from BaCO
3, CaCO
3, MgO or ZnO.
Preferably, the calcined temperature in the said step 1) is 1000 ℃～1300 ℃, and the pre-burning time is 2-4 hour.
Preferably, said step 1) and step 2) in ball-milling medium all be selected from absolute ethyl alcohol or deionized water, the ball milling time is 20～24 hours.
Preferably, said 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.
Said ball milling material is meant the raw material of ball milling, and the raw material of ball milling is by containing A element raw material, SrCO in step 1)
3, TiO
2And WO
3The mixing raw material that powder is formed, step 2) raw material of ball milling is the mixed powder of pre-burning in.
Preferably, the sticker in the said step 3) is that mass percent is 8%～10% polyvinyl alcohol water solution.
Preferably, the sticking treatment temperature of the row in the said step 4) is 550 ℃～600 ℃, and row is 4-10h in the sticking treatment time.
Preferably, the sintering temperature in the said step 4) is 1200 ℃～1500 ℃, and sintering time is 2～4 hours.
The present invention adopts traditional electronic ceramic technology, adopts AWO
4Mass ratio is composite modified; Development obtains can be used for the high Q value of adjustable microwave device, the barium-strontium titanate-based composite tungstate ceramic medium material that dielectric is adjustable, and the adjustable barium-strontium titanate-based composite tungstate ceramic medium material of dielectric of the present invention has following principal feature:
(1) Tc of this stupalith system can be with Ba/Sr and (1-x%) Ba
1-ySr
yTiO
3+ x%AWO
4(A=Ba, Ca, Mg, Zn; X=0～100; Y=0.4～0.6) mass ratio is adjustable continuously in very wide scope, can require the structure and the performance of adjustment material system according to the working temperature of the adjustable microwave device that is designed;
(2) through Ba/Sr and (1-x%) Ba
1-ySr
yTiO
3+ x%AWO
4(A=Ba, Ca, Mg, Zn; The span of x is 20≤x≤40; The span of y is 0.4≤y≤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) (Q value can up to 650), low specific inductivity (75); Higher adjustable rate (adjustable rate can up to 6.6%), and the specific inductivity seriation (that is: specific inductivity can through the numerical value that changes x regulate the mass percent of component and with the variation adjusting Ba of y value, the controllability that Sr recently reaches specific inductivity).
(4) its composition is with a cube Ba
1-ySr
yTiO
3Phase and cubic AWO
4Coexistence mutually has excellent microwave dielectric property;
(5) adopt traditional electronic ceramic technology, technology is simple, and cost is low, the spinoff of material system environment-protecting asepsis, and excellent performance is applicable to the material of adjustable microwave components and parts such as electronic tuning microwave resonator, wave filter and microwave-medium antenna.
Description of drawings
Fig. 1 is 65%Ba
0.5Sr
0.5TiO
3+ 35%ZnWO
4The X-ray diffraction analysis collection of illustrative plates of adjustable microwave ceramic dielectric material.
Fig. 2 is 65%Ba
0.5Sr
0.5TiO
3+ 35%MgWO
4The X-ray diffraction analysis collection of illustrative plates of adjustable microwave ceramic dielectric material.
Fig. 3 is 85%Ba
0.6Sr
0.4TiO
3+ 15%BaWO
4The X-ray diffraction analysis collection of illustrative plates of adjustable microwave ceramic dielectric material.
Fig. 4 is 50%Ba
0.4Sr
0.6TiO
3+ 50%CaWO
4The X-ray diffraction analysis collection of illustrative plates of adjustable microwave ceramic dielectric material.
Fig. 5 is 65%Ba
0.5Sr
0.5TiO
3+ 35%ZnWO
4The relation curve of the specific inductivity of adjustable microwave ceramic dielectric material and loss and temperature.
Fig. 6 is 65%Ba
0.5Sr
0.5TiO
3+ 35%MgWO
4The relation curve of the specific inductivity of adjustable microwave ceramic dielectric material and loss and temperature.
Fig. 7 is 85%Ba
0.6Sr
0.4TiO
3+ 15%BaWO
4The relation curve of the specific inductivity of adjustable microwave ceramic dielectric material and loss and temperature.
Fig. 8 is 50%Ba
0.4Sr
0.6TiO
3+ 50%CaWO
4The relation curve of the specific inductivity of adjustable microwave ceramic dielectric material and loss and temperature.
Fig. 9 is 65%Ba
0.5Sr
0.5TiO
3+ 35%ZnWO
4The specific inductivity of adjustable microwave ceramic dielectric material and the relation curve of strength of electric field.
Figure 10 is 65%Ba
0.5Sr
0.5TiO
3+ 35%MgWO
4The specific inductivity of adjustable microwave ceramic dielectric material and the relation curve of strength of electric field.
Figure 11 is 85%Ba
0.6Sr
0.4TiO
3+ 15%BaWO
4The specific inductivity of adjustable microwave ceramic dielectric material and the relation curve of strength of electric field.
Embodiment
The adjustable 65%Ba of the high Q electricity of embodiment 1 preparation
0.5Sr
0.5TiO
3+ 35%ZnWO
4Ceramic medium material
Respectively according to 65%Ba
0.5Sr
0.5TiO
3+ 35%ZnWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2With ZnO, 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%, the high-new inorganic materials in Foshan ltd) and ZnO (99.99%, Chemical Reagent Co., Ltd., Sinopharm Group), WO
3(99.8%, Alfa Aesar China LTD.)
Table 1.65%Ba
0.5Sr
0.5TiO
3+ 35%ZnWO
4The proportioning raw materials of ceramic medium material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | ZnO | WO 3 |
| Quality/g | 9.235 | 6.909 | 7.475 | 2.729 | 7.771 |
Above-mentioned powder is placed nylon ball grinder; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, discharging oven dry back was 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) and deionized water (mass ratio of deionized water and ball milling material is 3.0), ball milling 24 hours, discharging oven dry back powder is crossed 200 mesh sieves; According to traditional electronic ceramic technology, the Z 150PH (PVA) of employing 8% carries out granulation as sticker, 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 65%Ba
0.5Sr
0.5TiO
3+ 35%ZnWO
4Ceramics sample.The ceramics sample that makes is carried out thing phase and microstructure analysis earlier, to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing then, its relevant dielectric properties see Table 2.
Table 2.65%Ba0.5Sr0.5TiO
3+ 35%ZnWO
4The relevant dielectric properties of dielectric adjustable microwave ceramic dielectric material
In the present embodiment, 65%Ba
0.5Sr
0.5TiO
3+ 35%ZnWO
4The X-ray diffraction analysis collection of illustrative plates of dielectric adjustable microwave ceramic dielectric material is as shown in Figure 1.Result among Fig. 1 shows: its composition is with a cube Ba
0.5Sr
0.5TiO
3Phase and cubic ZnWO
4The phase structure coexistence.
In the present embodiment, 65%Ba0.5Sr0.5TiO
3+ 35%ZnWO
4The relation curve of the specific inductivity of dielectric adjustable microwave ceramic dielectric material and loss and temperature is as shown in Figure 5, and the result among Fig. 5 shows the compound ZnWO of stoichiometric ratio
4The Curie peak along with the increase of doping is moved to the low temperature direction rapidly.
In the present embodiment, 65%Ba0.5Sr0.5TiO
3+ 35%ZnWO
4The specific inductivity of dielectric adjustable microwave ceramic dielectric material and the relation curve of strength of electric field are as shown in Figure 9, and the test result among Fig. 9 shows with ZnWO
4Compoundly still have certain dielectric adjustable.Obtain very ideal microwave property after compound.
The high Q value of embodiment 2 preparations, the 65%Ba that dielectric is adjustable
0.5Sr
0.5TiO
3+ 35%MgWO
4Ceramic medium material
Respectively according to 65%Ba
0.5Sr
0.5TiO
3+ 35%MgWO
4Mole metering ratio, take by weighing BaCO
3, SrCO
3, TiO
2With MgO, WO
3Raw material (concrete quality is 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%, the high-new inorganic materials in Foshan ltd) and MgO (99.9%, Chemical Reagent Co., Ltd., Sinopharm Group), WO
3(99.8%, Alfa Aesar China LTD.)
Table 3.65%Ba
0.5Sr
0.5TiO
3+ 35%MgWO
4The proportioning raw materials of ceramic medium material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | MgO | WO 3 |
| Quality/g | 9.235 | 6.909 | 7.475 | 1.555 | 8.945 |
Above-mentioned powder is placed nylon ball grinder; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, discharging oven dry back was 1100 ℃～1300 ℃ pre-burnings 4 hours; Powder after the grinding places nylon ball grinder; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, discharging oven dry back powder is crossed 200 mesh sieves; According to traditional electronic ceramic technology, the Z 150PH (PVA) of employing 10% carries out granulation as sticker, 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 65%Ba
0.5Sr
0.5TiO
3+ 35%ZnWO
4Ceramics sample.The ceramics sample that makes is carried out thing phase and microstructure analysis earlier, to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing then, its relevant dielectric properties see Table 4.
Table 4.65%Ba
0.5Sr
0.5TiO
3+ 35%MgWO
4The relevant dielectric properties of dielectric adjustable microwave ceramic dielectric material
In the present embodiment, 65%Ba
0.5Sr
0.5TiO
3+ 35%MgWO
4The X-ray diffraction analysis collection of illustrative plates of dielectric adjustable microwave ceramic dielectric material is as shown in Figure 2, and the result among the figure shows that its composition is with a cube Ba
0.5Sr
0.5TiO
3Phase and cubic MgWO
4The phase structure coexistence.
In the present embodiment, 65%Ba
0.5Sr
0.5TiO
3+ 35%MgWO
4The relation curve of the specific inductivity of dielectric adjustable microwave ceramic dielectric material and loss and temperature is as shown in Figure 6, and the result among the figure shows the compound MgWO of stoichiometric ratio
4The Curie peak is along with the increase of doping is moved to the low temperature direction rapidly.
In the present embodiment, 65%Ba
0.5Sr
0.5TiO
3+ 35%MgWO
4The specific inductivity of dielectric adjustable microwave ceramic dielectric material and the relation curve of strength of electric field are shown in figure 10, and test result shows with MgWO
4Compoundly still have certain dielectric adjustable, compound back obtains more satisfactory microwave property.
Embodiment 3 preparation 85.0%Ba
0.6Sr
0.4TiO
3+ 15.0%BaWO
4Ceramic medium material
Respectively according to 85.0%Ba
0.6Sr
0.4TiO
3+ 15.0%BaWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2With MgO, WO
3Raw material.
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 ltd) and WO
3(99.8%, Alfa Aesar China LTD.)
Table 5.85.0%Ba
0.6Sr
0.4TiO
3+ 15.0%BaWO
4The proportioning raw materials of ceramic medium material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | WO 3 |
| Quality/g | 14.382 | 9.035 | 9.775 | 2.709 |
Above-mentioned powder is placed nylon ball grinder; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, discharging oven dry back was 1000 ℃～1200 ℃ pre-burnings 4 hours; Powder after the grinding places nylon ball grinder; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, discharging oven dry back powder is crossed 200 mesh sieves; According to traditional electronic ceramic technology, the Z 150PH (PVA) of employing 8% carries out granulation as sticker, 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 85.0%Ba
0.6Sr
0.4TiO
3+ 15.0%BaWO
4Ceramics sample.The ceramics sample that makes is carried out thing phase and microstructure analysis earlier, to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing then, its relevant dielectric properties see Table 6.
Table 6.85%Ba
0.6Sr
0.4TiO
3+ 15%BaWO
4The relevant dielectric properties of dielectric adjustable microwave ceramic dielectric material
In the present embodiment, 85%Ba
0.6Sr
0.4TiO
3+ 15%BaWO
4The X-ray diffraction analysis collection of illustrative plates of dielectric adjustable microwave ceramic dielectric material is as shown in Figure 3.Result among Fig. 3 shows: its composition is with a cube Ba
0.6Sr
0.4TiO
3Phase and cubic BaWO
4The phase structure coexistence.
In the present embodiment, 85%Ba
0.6Sr
0.4TiO
3+ 15%BaWO
4The relation curve of the specific inductivity of dielectric adjustable microwave ceramic dielectric material and loss and temperature is as shown in Figure 7, and the result among Fig. 7 shows the compound BaWO of stoichiometric ratio
4The Curie peak along with the increase of doping is moved and not obvious to the low temperature direction, show that this embodiment has dielectric adjustable preferably.
In the present embodiment, 85%Ba
0.5Sr0.5TiO
3+ 15%BaWO
4The specific inductivity of dielectric adjustable microwave ceramic dielectric material and the relation curve of strength of electric field are shown in figure 11, and the test result among Figure 11 shows with BaWO
4Compoundly have a better dielectric adjustable.
Embodiment 4 preparation 50.0%Ba
0.4Sr
0.6TiO
3+ 50.0%CaWO
4Ceramic medium material
Respectively according to 50.0%Ba
0.4Sr
0.6TiO
3+ 50.0%CaWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2And CaCO
3, WO
3Raw material.
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 ltd) and CaCO
3(99.99%, Chemical Reagent Co., Ltd., Sinopharm Group), WO
3(99.8%, Alfa Aesar China LTD.)
Table 8.50.0%Ba
0.4Sr
0.6TiO
3+ 50.0%CaWO
4The proportioning raw materials of ceramic medium material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | CaCO 3 | WO 3 |
| Quality/g | 5.822 | 6.533 | 5.891 | 5.215 | 12.078 |
Above-mentioned powder is placed nylon ball grinder; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, discharging oven dry back was 1000 ℃～1200 ℃ pre-burnings 4 hours; Powder after the grinding places nylon ball grinder; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, discharging oven dry back powder is crossed 200 mesh sieves; According to traditional electronic ceramic technology, the Z 150PH (PVA) of employing 8% carries out granulation as sticker, 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 50.0%Ba
0.4Sr
0.6TiO
3+ 50.0%CaWO
4Ceramics sample.The ceramics sample that makes is carried out thing phase and microstructure analysis earlier, to its polishing both surfaces, quilt silver, carry out the dielectric properties test behind the silver ink firing then, its relevant dielectric properties see Table 8.
Table 8.50%Ba
0.4Sr
0.6TiO
3+ 50%CaWO
4The relevant dielectric properties of dielectric adjustable microwave ceramic dielectric material
In the present embodiment, 50%Ba
0.4Sr
0.6TiO
3+ 50%CaWO
4The X-ray diffraction analysis collection of illustrative plates of dielectric adjustable microwave ceramic dielectric material is as shown in Figure 4.Result among Fig. 4 shows: its composition is with a cube Ba
0.5Sr
0.5TiO
3Phase and cubic CaWO
4The phase structure coexistence.
In the present embodiment, 50%Ba
0.4Sr
0.6TiO
3+ 50%CaWO
4The relation curve of the specific inductivity of dielectric adjustable microwave ceramic dielectric material and loss and temperature is as shown in Figure 8, and the result among Fig. 8 shows stoichiometric ratio complex Ca WO
4The Curie peak along with the increase of doping is moved to the low temperature direction rapidly.
In the present embodiment, 50%Ba
0.4Sr
0.6TiO
3+ 50%CaWO
4The specific inductivity of dielectric adjustable microwave ceramic dielectric material and the relation curve of strength of electric field are shown in figure 12, and the test result among Figure 12 shows with CaWO
4The unusual ideal microwave property of compound acquisition.
The adjustable 95%Ba of the high Q electricity of embodiment 5 preparations
0.5Sr
0.5TiO
3+ 5%ZnWO
4Ceramic medium material
Respectively according to 95%Ba
0.5Sr
0.5TiO
3+ 5%ZnWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2With ZnO, 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 ltd) and ZnO (99.99%, Chemical Reagent Co., Ltd., Sinopharm Group), WO
3(99.8%, Alfa Aesar China LTD.)
Table 9.95%Ba
0.5Sr
0.5TiO
3+ 5%ZnWO
4The proportioning raw materials of ceramic medium material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | ZnO | WO 3 |
| Quality/g | 13.497 | 10.098 | 10.925 | 0.390 | 1.110 |
Above-mentioned powder is placed nylon ball grinder; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, discharging oven dry back was 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) and deionized water (mass ratio of deionized water and ball milling material is 3.0), ball milling 24 hours, discharging oven dry back powder is crossed 200 mesh sieves; According to traditional electronic ceramic technology, the Z 150PH (PVA) of employing 8% carries out granulation as sticker, 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 95%Ba
0.5Sr
0.5TiO
3+ 5%ZnWO
4Ceramics sample.Through test, the ceramic medium material that makes in the present embodiment has high Q value, low specific inductivity, higher characteristics such as adjustable rate.
The adjustable 80%Ba of the high Q electricity of embodiment 6 preparations
0.5Sr
0.5TiO
3+ 20%ZnWO
4Ceramic medium material
Respectively according to 80%Ba
0.5Sr
0.5TiO
3+ 20%ZnWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2With ZnO, 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 ltd) and ZnO (99.99%, Chemical Reagent Co., Ltd., Sinopharm Group), WO
3(99.8%, Alfa Aesar China LTD.)
Table 10.80%Ba
0.5Sr
0.5TiO
3+ 20%ZnWO
4The proportioning raw materials of ceramic medium material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | ZnO | WO 3 |
| Quality/g | 11.366 | 9.200 | 8.0 | 1.559 | 4.441 |
Above-mentioned powder is placed nylon ball grinder; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, discharging oven dry back was 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) and deionized water (mass ratio of deionized water and ball milling material is 3.0), ball milling 24 hours, discharging oven dry back powder is crossed 200 mesh sieves; According to traditional electronic ceramic technology, the Z 150PH (PVA) of employing 8% carries out granulation as sticker, 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 80%Ba
0.5Sr
0.5TiO
3+ 20%ZnWO
4Ceramics sample.Through test, the ceramic medium material that makes in the present embodiment has high Q value, low specific inductivity, higher characteristics such as adjustable rate.
The adjustable 60%Ba of the high Q electricity of embodiment 7 preparations
0.5Sr
0.5TiO
3+ 40%ZnWO
4Ceramic medium material
Respectively according to 60%Ba
0.5Sr
0.5TiO
3+ 40%ZnWO
4The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2With ZnO, 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 ltd) and ZnO (99.99%, Chemical Reagent Co., Ltd., Sinopharm Group), WO
3(99.8%, Alfa Aesar China LTD.)
Table 11.60%Ba
0.5Sr
0.5TiO
3+ 40%ZnWO
4The proportioning raw materials of ceramic medium material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | ZnO | WO 3 |
| Quality/g | 8.525 | 6.377 | 6.900 | 3.119 | 8.881 |
Above-mentioned powder is placed nylon ball grinder; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, discharging oven dry back was 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) and deionized water (mass ratio of deionized water and ball milling material is 3.0), ball milling 24 hours, discharging oven dry back powder is crossed 200 mesh sieves; According to traditional electronic ceramic technology, the Z 150PH (PVA) of employing 8% carries out granulation as sticker, 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 60%Ba
0.5Sr
0.5TiO
3+ 40%ZnWO
4Ceramics sample.Through test, the ceramic medium material that makes in the present embodiment has high Q value, low specific inductivity, higher characteristics such as adjustable rate.
Claims (7)
1. barium-strontium titanate-based composite tungstate ceramic medium material that dielectric is adjustable, its component is:
(1-x%) Ba
1-ySr
yTiO
3+ x%AWO
4Wherein, A is selected from Ca, Mg or Zn, and x% is weight percentage; Span is 5wt%≤x%≤50wt%; The span of y is 0.4≤y≤0.6, and the preparation method of the barium-strontium titanate-based composite tungstate ceramic medium material that said dielectric is adjustable comprises the steps:
1) selects for use and contain A element material powder, SrCO
3Powder, TiO
2Powder and WO
3Powder is as main raw material, according to (1-x%) Ba
1-ySr
yTiO
3+ x%AWO
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) add zirconia ball and ball-milling medium in the mixed powder that in step 1), makes, sieve after ball milling and the discharging oven dry;
3) adopt sticker to step 2) in powder after sieving carry out granulation, compression moulding ceramic green sheet then;
4) the ceramic green sheet that makes in the step 3) is carried out sintering after arranging sticking the processing, sintering temperature is 1200 ℃～1500 ℃, and sintering time is 2～4 hours, can obtain said barium-strontium titanate-based composite tungstate ceramic medium material.
2. the adjustable barium-strontium titanate-based composite tungstate ceramic medium material of dielectric described in claim 1 is characterized in that, the A element raw material that contains in the said step 1) is selected from CaCO
3, MgO or ZnO.
3. the adjustable barium-strontium titanate-based composite tungstate ceramic medium material of dielectric described in claim 1 is characterized in that, the calcined temperature in the said step 1) is 1000 ℃～1300 ℃, and the pre-burning time is 2-4 hour.
4. the adjustable barium-strontium titanate-based composite tungstate ceramic medium material of dielectric described in claim 1 is characterized in that said step 1) and step 2) in ball-milling medium all be selected from absolute ethyl alcohol or deionized water, the ball milling time is 20～24 hours.
5. the adjustable barium-strontium titanate-based composite tungstate ceramic medium material of dielectric described in claim 1 is characterized in that, the sticker in the said step 3) is that mass percent is 8%～10% polyvinyl alcohol water solution.
6. the adjustable barium-strontium titanate-based composite tungstate ceramic medium material of dielectric described in claim 1 is characterized in that, the sticking treatment temperature of the row in the said step 4) is 550 ℃～600 ℃, and row is 4～10h the sticking time of handling.
7. be used to prepare the adjustable microwave components and parts like the adjustable barium-strontium titanate-based composite tungstate ceramic medium material of the arbitrary said dielectric of claim 1-6.
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| 李俊 等.BaWO4/(Ba，Sr)TiO3复合陶瓷的显微结构与介电性能.《复合材料学报》.2009,第26卷(第2期),120-124. * |
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