CN101955356B - Tunable dielectric barium strontium titanate based composite silicate microwave dielectric material and preparation thereof - Google Patents
Tunable dielectric barium strontium titanate based composite silicate microwave dielectric material and preparation thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electronic materials and devices, and discloses a tunable dielectric barium strontium titanate based composite silicate ceramic dielectric material and preparation thereof. The tunable dielectric barium strontium titanate based composite silicate ceramic dielectric material has a component formula of (1-m%)Ba1-zSrzTiO3+m%(Sr1-xAx)2(Zn1-yBy)Si2O7, wherein A is selected from Ba or Ca; B is selected from Co, Mg, Mn or Ni; the numerical value range of x is not smaller than 0 and not more than 1; the numerical value range of y is not smaller than 0 and not more than 1; the numerical value range of z is not smaller than 0.4 and not more than 0.6; and the numerical value range of m% is more than 0wt% and smaller than 100wt%. The tunable dielectric barium strontium titanate based composite silicate ceramic dielectric material of the invention is high in Q (Quality) value, low in dielectric constant and high in dielectric tunable rate, and can be widely applied to preparation of tunable microwave elements and devices such as electric tuning microwave tuners, filters, microwave dielectric antennae and the like.
Description
Technical field
The invention belongs to electronic material and device technology field, be specifically related to a kind of dielectric adjustable barium-strontium titanate-based composition silicate microwave dielectric material 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 of high dielectric tunable characteristic 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 Xiujian Chou of Tongji 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=190, Q=189, T=18.1).Yet the over-all properties of this system awaits further to improve.Relevant report is not seen in the micro-wave dielectric tunable characteristic research of strontium-barium titanate complex silicate salt material as yet.
Summary of the invention
The purpose of this invention is to provide a kind of dielectric adjustable barium-strontium titanate-based composition silicate ceramic medium material and preparation thereof, the barium-strontium titanate-based composition silicate ceramic medium material that this dielectric is adjustable has high Q value and the adjustable characteristic of dielectric.
The barium-strontium titanate-based composition silicate ceramic medium material that dielectric of the present invention is adjustable, the chemical general formula of its component is: (1-m%) Ba
1-zSr
zTiO
3+ m% (Sr
1-xA
x)
2(Zn
1-yB
y) Si
2O
7Wherein, A is selected from Ba or Ca, and B is selected from Co, Mg, Mn or Ni; The span of x is 0≤x≤1; The span of y is 0≤y≤1; The span of z is 0.4≤z≤0.6; The span of m is 0wt%＜m%＜100wt%.
Preferably, the span of x is 0.1≤x≤0.6; 0≤y≤0.5; 0.4≤z≤0.6; 40wt%≤m%≤60wt%.
Preferred, said 0.1≤x≤0.6, y=0, z=0.5, m%=60wt%; The component general formula that is the adjustable barium-strontium titanate-based composition silicate ceramic medium material of said dielectric is: 40%Ba
0.5Sr
0.5TiO
3+ 60% (Sr
1-xBa
x)
2ZnSi
2O
7
In the component general formula of the barium-strontium titanate-based composition silicate 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 m% representative is in the total mass of said barium-strontium titanate-based composition silicate ceramic medium material, said (Sr
1-xA
x)
2(Zn
1-yB
y) Si
2O
7Mass percent; (1-m) the % representative is in the total mass of said barium-strontium titanate-based composition silicate ceramic medium material, said Ba
1-zSr
zTiO
3Mass percent.
The preparation method of the barium-strontium titanate-based composition silicate 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 BaCO for use
3Powder, SrCO3 powder, TiO2 powder, SiO
2Powder, ZnO powder, ACO
3The oxide compound of powder and B or carbonate powder are as main raw material, according to (1-m%) Ba
1-zSr
zTiO
3+ m% (Sr
1-xA
x)
2(Zn
1-yB
y) Si
2O
7The stoichiometric ratio batching of middle Ba, Sr, Ti, Si, Zn, A and B places nylon ball grinder with confected materials, carries out ball milling behind adding zirconia ball and the ball-milling medium, and the discharging oven dry is after obtain mixed powder after pre-burning and the grinding;
Preferable, said calcined temperature is 1000 ℃～1300 ℃, the pre-burning time is 2～4 hours; Further, said calcined temperature is 1000～1200 ℃.
2) add zirconia ball and ball-milling medium ball milling in the mixed powder that in step 1), makes, sieve after the discharging oven dry;
Preferable, the order number of said sieve is 100～300 orders, further, the order number of said sieve is 200 orders.
3) adopt sticker to step 2) in powder after sieving carry out granulation, press down at 10MPa～100MPa pressure and process the ceramic green sheet;
Preferable, said sticker is that mass percent is 8%～10% Z 150PH (PVA) aqueous solution.
4) the ceramic green sheet that makes in the step 3) is carried out sintering after arranging sticking the processing, obtain said barium-strontium titanate-based composition silicate ceramic medium material.
Preferable, the sticking treatment temperature of row described in the step 4) is 550 ℃～600 ℃, soaking time is 4～10h; Said agglomerating temperature is 1200 ℃～1500 ℃, and sintering time is 4～10 hours.Further, the sticking treatment temperature of said row is 550 ℃; Said agglomerating temperature is 1230 ℃～1380 ℃.
Preferably, said step 1) and step 2) in time of ball milling be 20～24 hours, ball-milling medium all is selected from absolute ethyl alcohol or deionized water.
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 CaCO in step 1)
3Powder, Co
2O
3Powder, MgO powder, MnCO
3Powder, NiO powder, BaCO
3, SrCO
3And TiO
2The mixing raw material that powder is formed, step 2) raw material of ball milling is the mixed powder of pre-burning in.
The present invention adopts traditional electronic ceramic technology, according to Ba
1-zSr
zTiO
3With (Sr
1-xA
x)
2(Zn
1-yB
y) Si
2O
7Mass ratio carry out compound; Development obtains can be used for the high Q value of adjustable microwave device, the barium-strontium titanate-based composition silicate ceramic medium material that high dielectric is adjustable, and the adjustable barium-strontium titanate-based composition silicate ceramic medium material of dielectric of the present invention has following principal feature:
(1) Tc of this stupalith system can be with Ba/Sr, Ca/Sr and (1-m%) Ba
1-zSr
zTiO
3+ m% (Sr
1-xA
x)
2(Zn
1-yB
y) Si
2O
7(A=Ba or Ca; B=Co, Mg, Mn or Ni; X=0～1; Y=0～1; Z=0.4～0.6; 0wt%＜m%＜100wt%) 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, Ca/Sr and (1-m%) Ba
1-zSr
zTiO
3+ m% (Sr
1-xA
x)
2(Zn
1-yB
y) Si
2O
7(A=Ba or Ca; B=Co, Mg, Mn or Ni; X=0～1; Y=0～1; Z=0.4～0.6; M%=5wt%～80wt%) the 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) (the Q value can reach 417), low specific inductivity (152); Higher adjustable rate (adjustable rate can reach 16%), and the specific inductivity seriation (that is: specific inductivity can through the numerical value that changes m regulate component mass percent and with the variation of x, z value regulate Ca, Sr compares and Ba, Sr recently reach the controllability of specific inductivity).
(4) its composition is with Ba
1-zSr
zTiO
3Mutually with (Sr
1-xA
x)
2(Zn
1-yB
y) Si
2O
7Coexistence 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 40%Ba
0.5Sr
0.5TiO
3+ 60%BaSrZnSi
2O
7The X-ray diffraction analysis collection of illustrative plates of adjustable microwave ceramic dielectric material.
Fig. 2 is 40%Ba
0.5Sr
0.5TiO
3+ 60%BaSrZnSi
2O
7The relation curve of the specific inductivity of adjustable microwave ceramic dielectric material and loss and temperature.
Fig. 3 is 40%Ba
0.5Sr
0.5TiO
3+ 60%BaSrZnSi
2O
7The specific inductivity of adjustable microwave ceramic dielectric material and the relation curve of strength of electric field.
Fig. 4 is 60%Ba
0.4Sr
0.6TiO
3+ 40% (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7The X-ray diffraction analysis collection of illustrative plates of adjustable microwave ceramic dielectric material.
Fig. 5 is 60%Ba
0.4Sr
0.6TiO
3+ 40% (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7The relation curve of the specific inductivity of adjustable microwave ceramic dielectric material and loss and temperature.
Fig. 6 is 60%Ba
0.4Sr
0.6TiO
3+ 40% (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7The specific inductivity of adjustable microwave ceramic 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 to the present invention is described and are not used in restriction protection scope of the present invention.
The high Q value of embodiment 1 preparation, the 40%Ba that dielectric is adjustable
0.5Sr
0.5TiO
3+ 60% (Sr
0.5Ba
0.5)
2ZnSi
2O
7Ceramic medium material
Respectively according to 40%Ba
0.5Sr
0.5TiO
3+ 60%BaSrZnSi
2O
7The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2With ZnO, SiO
2Raw material (as shown in table 1).
Raw material sources: BaCO
3(99.8%, Alfa Aesar China LTD.), SrCO
3(99.0%, Alfa Aesar China LTD.), TiO
2(99.9%, the high-new inorganic materials in Foshan ltd) and ZnO (99.99%, Chemical Reagent Co., Ltd., Sinopharm Group), SiO
2(99.9%, Chemical Reagent Co., Ltd., Sinopharm Group).
Table 1.40%Ba
0.5Sr
0.5TiO
3+ 60%BaSrZnSi
2O
7The proportioning raw materials of ceramic medium material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | ZnO | SiO 2 |
| Quality/g | 13.459 | 10.148 | 4.605 | 3.196 | 4.722 |
With above-mentioned powder according to Ba
0.5Sr
0.5TiO
3And BaSrZnSi
2O
7Batching is placed in the nylon ball grinder respectively; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, pre-burning 4 hours under the temperature of 1200 ℃ and 1000 ℃ respectively after discharging is dried; 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, 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 10 hours, sample is under air atmosphere through 550 ℃ of sticking processing of row, and sintering temperature is 1230 ℃, is incubated after 4 hours, obtains 40%Ba
0.5Sr
0.5TiO
3+ 60%BaSrZnSi
2O
7Ceramics 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 2.40%Ba
0.5Sr
0.5TiO
3+ 60%BaSrZnSi
2O
7The relevant dielectric properties of dielectric adjustable microwave ceramic dielectric material
In the present embodiment, 40%Ba
0.5Sr
0.5TiO
3+ 60%BaSrZnSi
2O
7The 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 Ba
0.5Sr
0.5TiO
3Phase and BaSrZnSi
2O
7The phase structure coexistence.
In the present embodiment, 40%Ba
0.5Sr
0.5TiO
3+ 60%BaSrZnSi
2O
7The relation curve of the specific inductivity of dielectric adjustable microwave ceramic dielectric material and loss and temperature is as shown in Figure 2, and the result among Fig. 2 shows the compound BaSrZnSi of stoichiometric ratio
2O
7The Curie peak not along with the increase of compounding quantity continues to move to the low temperature direction.It is very little that loss keeps in long TR.
In the present embodiment, 40%Ba
0.5Sr
0.5TiO
3+ 60%BaSrZnSi
2O
7The specific inductivity of dielectric adjustable microwave ceramic dielectric material and the relation curve of strength of electric field are as shown in Figure 3, and the test result among Fig. 3 shows with BaSrZnSi
2O
7Compoundly have a higher dielectric adjustable.Obtain the very comprehensive microwave dielectric property of ideal after compound.
The high Q value of embodiment 2 preparations, the 60%Ba that dielectric is adjustable
0.4Sr
0.6TiO
3+ 40% (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7Ceramic medium material
Respectively according to 60%Ba
0.4Sr
0.6TiO
3+ 40% (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7Mole metering ratio, take by weighing BaCO
3, SrCO
3, TiO
2With ZnO, Co
2O
3, SiO
2Raw 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 China LTD.), TiO
2(99.9%, the high-new inorganic materials in Foshan ltd) and ZnO (99.9%, Chemical Reagent Co., Ltd., Sinopharm Group), Co
2O
3(99.9%, Chemical Reagent Co., Ltd., Sinopharm Group), SiO
2(99.9%, Chemical Reagent Co., Ltd., Sinopharm Group).
Table 3.60%Ba
0.4Sr
0.6TiO
3+ 40% (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7The proportioning raw materials of ceramic medium material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | ZnO | Co 2O 3 | SiO 2 |
| Quality/g | 13.083 | 10.977 | 7.076 | 1.984 | 0.213 | 3.083 |
With above-mentioned powder according to Ba
0.4Sr
0.6TiO
3(Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7Batching is placed in the nylon ball grinder respectively; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, pre-burning 4 hours under the temperature of 1100 ℃ and 1000 ℃ respectively after discharging is dried; 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 absolute ethyl alcohol or deionized water (mass ratio of water-ethanol or deionized water and ball milling material is 1.5: 1), 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 10 hours, sample is under air atmosphere through 550 ℃ of sticking processing of row, and sintering temperature is 1350 ℃, is incubated after 6 hours, obtains 60%Ba
0.4Sr
0.6TiO
3+ 40% (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7Ceramics 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 4.60%Ba
0.4Sr
0.6TiO
3+ 40% (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7The relevant dielectric properties of dielectric adjustable microwave ceramic dielectric material
In the present embodiment, 60%Ba
0.4Sr
0.6TiO
3+ 40% (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7The 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 Ba
0.4Sr
0.6TiO
3Mutually with (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7The phase structure coexistence.
In the present embodiment, 60%Ba
0.4Sr
0.6TiO
3+ 40% (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7The 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 that the Curie peak is along with the increase of compounding quantity continues to move to the low temperature direction in the stoichiometric ratio compound system.It is very little that loss keeps in long TR.
In the present embodiment, 60%Ba
0.4Sr
0.6TiO
3+ 40% (Sr
0.4Ba
0.6)
2(Zn
0.95Co
0.05) Si
2O
7The specific inductivity of dielectric adjustable microwave ceramic dielectric material and the relation curve of strength of electric field are as shown in Figure 6, and the test result among Fig. 6 shows the higher dielectric adjustable of maintenance in this compound system.Obtain the very comprehensive microwave dielectric property of ideal after compound.
The adjustable 50%Ba of the high Q electricity of embodiment 3 preparations
0.5Sr
0.5TiO
3+ 50% (Sr
0.9Ca
0.1)
2(Zn
0.5Mg
0.5) Si
2O
7Ceramic medium material.
Respectively according to 50%Ba
0.5Sr
0.5TiO
3+ 50% (Sr
0.9Ca
0.1)
2(Zn
0.5Mg
0.5) Si
2O
7The mole proportioning, take by weighing BaCO
3, SrCO
3, TiO
2With ZnO, MgO, SiO
2Raw material (as shown in table 5).
Raw material sources: BaCO
3(99.8%, Alfa Aesar China LTD.), SrCO
3(99.0%, Alfa Aesar China LTD.), TiO
2(99.9%, the high-new inorganic materials in Foshan ltd) and ZnO (99.99%, Chemical Reagent Co., Ltd., Sinopharm Group), MgO (99.9%, Chemical Reagent Co., Ltd., Sinopharm Group), SiO
2(99.9%, Chemical Reagent Co., Ltd., Sinopharm Group).
Table 5.50%Ba
0.5Sr
0.5TiO
3+ 50% (Sr
0.9Ca
0.1)
2(Zn
0.5Mg
0.5) Si
2O
7The proportioning raw materials of ceramic medium material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | ZnO | MgO | SiO 2 |
| Quality/g | 7.118 | 15.998 | 5.756 | 1.612 | 0.799 | 4.764 |
With above-mentioned powder according to Ba
0.5Sr
0.5TiO
3(Sr
0.9Ca
0.1)
2(Zn
0.5Mg
0.5) preparing burden respectively is placed in the nylon ball grinder; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, the pre-burning of pre-burning under the temperature of 1200 ℃ and 1000 ℃ respectively after discharging is dried 2 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 10 hours, sample is under air atmosphere through 550 ℃ of sticking processing of row, and sintering temperature is 1380 ℃, is incubated after 10 hours, obtains 50%Ba
0.5Sr
0.5TiO
3+ 50% (Sr
0.9Ca
0.1)
2(Zn
0.5Mg
0.5) Si
2O
7Ceramics 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 6.50%Ba
0.5Sr
0.5TiO
3+ 50% (Sr
0.9Ca
0.1)
2(Zn
0.5Mg
0.5) Si
2O
7The relevant dielectric properties of dielectric adjustable microwave ceramic dielectric material
In the present embodiment, 50%Ba
0.5Sr
0.5TiO
3+ 50% (Sr
0.9Ca
0.1)
2(Zn
0.5Mg
0.5) Si
2O
7The composition of dielectric adjustable microwave ceramic dielectric material is with Ba
0.5Sr
0.5TiO
3Mutually with (Sr
0.9Ca
0.1)
2(Zn
0.5Mg
0.5) Si
2O
7The phase structure coexistence.
In the present embodiment, 50%Ba
0.5Sr
0.5TiO
3+ 50% (Sr
0.9Ca
0.1)
2(Zn
0.5Mg
0.5) Si
2O
7The Curie peak is along with the increase of compounding quantity continues to move to the low temperature direction in the compound system.It is very little that loss keeps in long TR.
In the present embodiment, 50%Ba
0.5Sr
0.5TiO
3+ 50% (Sr
0.9Ca
0.1)
2(Zn
0.5Mg
0.5) Si
2O
7Keep higher dielectric adjustable in the compound system.Obtain the very comprehensive microwave dielectric property of ideal after compound.
The high Q value of embodiment 4 preparations, the 45%Ba that dielectric is adjustable
0.6Sr
0.4TiO
3+ 55% (Sr
0.5Ba
0.5)
2(Zn
0.9Mn
0.1) Si
2O
7Ceramic medium material
Respectively according to 45%Ba
0.6Sr
0.4TiO
3+ 55% (Sr
0.5Ba
0.5)
2(Zn
0.9Mn
0.1) Si
2O
7Mole metering ratio, take by weighing BaCO
3, SrCO
3, TiO
2With ZnO, MnCO
3, SiO
2Raw material (concrete quality is as shown in table 7).
Raw material sources: BaCO
3(99.8%, Alfa Aesar China LTD.), SrCO
3(99.0%, Alfa Aesar China LTD.), TiO
2(99.9%, the high-new inorganic materials in Foshan ltd) and ZnO (99.9%, Chemical Reagent Co., Ltd., Sinopharm Group), MnCO
3(99.9%, Chemical Reagent Co., Ltd., Sinopharm Group), SiO
2(99.9%, Chemical Reagent Co., Ltd., Sinopharm Group).
Table 7.45%Ba
0.6Sr
0.4TiO
3+ 55% (Sr
0.5Ba
0.5)
2(Zn
0.9Mn
0.1) Si
2O
7The proportioning raw materials of ceramic medium material
| Prescription | BaCO 3 | SrCO 3 | TiO 2 | ZnO | MnCO 3 | SiO 2 |
| Quality/g | 14.640 | 9.153 | 5.060 | 2.645 | 0.343 | 4.339 |
With above-mentioned powder according to 45%Ba
0.6Sr
0.4TiO
3+ 55% (Sr
0.5Ba
0.5)
2(Zn
0.9Mn
0.1) Si
2O
7Batching is placed in the nylon ball grinder respectively; Add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 24 hours, pre-burning 4 hours under the temperature of 1200 ℃ and 1000 ℃ respectively after discharging is dried; 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 absolute ethyl alcohol or deionized water (mass ratio of water-ethanol or deionized water and ball milling material is 1.5: 1), 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 10 hours, sample is under air atmosphere through 550 ℃ of sticking processing of row, and sintering temperature is 1350 ℃, is incubated after 6 hours, obtains 45%Ba
0.6Sr
0.4TiO
3+ 55% (Sr
0.5Ba
0.5)
2(Zn
0.9Mn
0.1) Si
2O
7Ceramics 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 8.45%Ba
0.6Sr
0.4TiO
3+ 55% (Sr
0.5Ba
0.5)
2(Zn
0.9Mn
0.1) Si
2O
7The relevant dielectric properties of dielectric adjustable microwave ceramic dielectric material
In the present embodiment, 45%Ba
0.6Sr
0.4TiO
3+ 55% (Sr
0.5Ba
0.5)
2(Zn
0.9Mn0.1) Si
2O
7The 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 Ba
0.4Sr
0.6TiO
3Mutually with (Sr
0.5Ba
0.5)
2(Zn
0.9Mn
0.1) Si
2O
7The phase structure coexistence.
In the present embodiment, 45%Ba
0.6Sr
0.4TiO
3+ 55% (Sr
0.5Ba
0.5)
2(Zn
0.9Mn
0.1) Si
2O
7The 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 that the Curie peak is along with the increase of compounding quantity continues to move to the low temperature direction in the stoichiometric ratio compound system.It is very little that loss keeps in long TR.
In the present embodiment, 45%Ba
0.6Sr
0.4TiO
3+ 55% (Sr
0.5Ba
0.5)
2(Zn
0.9Mn
0.1) Si
2O
7Keep higher dielectric adjustable in the compound system.Obtain the very comprehensive microwave dielectric property of ideal after compound.
Claims (8)
1. barium-strontium titanate-based composition silicate ceramic medium material that dielectric is adjustable, the general formula of its component is: the chemical general formula of its component is: (1-m%) Ba
1-zSr
zTiO
3+ m% (Sr
1-xA
x)
2(Zn
1-yB
y) Si
2O
7Wherein, A is selected from Ba or Ca, and B is selected from Co, Mg or Mn; The span of x is 0.1≤x≤0.6; The span of y is 0≤y≤0.5; The span of z is 0.4≤z≤0.6; The span of m is 40wt%≤m%≤60wt%.
2. the preparation method of the adjustable barium-strontium titanate-based composition silicate ceramic medium material of dielectric according to claim 1 comprises the steps:
1), selects BaCO for use
3Powder, SrCO
3Powder, TiO
2Powder, SiO
2Powder, ZnO powder, ACO
3The oxide compound of powder and B or carbonate powder are as main raw material, according to (1-m%) Ba
1-zSr
zTiO
3+ m% (Sr
1-xA
x)
2(Zn
1-yB
y) Si
2O
7The stoichiometric ratio batching of middle Ba, Sr, Ti, Si, Zn, A and B places nylon ball grinder with confected materials, carries out ball milling behind adding zirconia ball and the ball-milling medium, and the discharging oven dry is after obtain mixed powder after pre-burning and the grinding;
2), the mixed powder that in step 1), makes, add zirconia ball and ball-milling medium ball milling, discharging is sieved after drying;
3), adopt sticker to step 2) in powder after sieving carry out granulation, press down at 10MPa～100MPa pressure and process the ceramic green sheet;
4), the ceramic green sheet that makes in the step 3) is carried out sintering through row is sticking after handling, obtain said barium-strontium titanate-based composition silicate ceramic medium material.
3. the preparation method of the adjustable barium-strontium titanate-based composition silicate ceramic medium material of dielectric described in claim 2 is characterized in that in the step 1), calcined temperature is 1000 ℃～1300 ℃, and the pre-burning time is 2～4h.
4. the preparation method of the adjustable barium-strontium titanate-based composition silicate ceramic medium material of dielectric described in claim 2; It is characterized in that; Said step 1) and step 2) in the ball milling time be 20～24 hours, ball-milling medium all is selected from absolute ethyl alcohol or deionized water.
5. the preparation method of the adjustable barium-strontium titanate-based composition silicate ceramic medium material of dielectric described in claim 2 is characterized in that sticker is that mass percent is 8%～10% polyvinyl alcohol water solution in the said step 3).
6. the preparation method of the adjustable barium-strontium titanate-based composition silicate ceramic medium material of dielectric described in claim 2 is characterized in that, the sticking treatment temperature of the row in the said step 4) is 550 ℃～600 ℃, and soaking time is 4～10 hours.
7. the preparation method of the adjustable barium-strontium titanate-based composition silicate ceramic medium material of dielectric described in claim 2 is characterized in that the sintering temperature in the said step 4) is 1200 ℃～1500 ℃, and sintering time is 4～10 hours.
8. the barium-strontium titanate-based composition silicate ceramic medium material that dielectric as claimed in claim 1 is adjustable is used to prepare the adjustable microwave components and parts.
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| CN103771842B (en) * | 2014-01-10 | 2015-05-27 | 电子科技大学 | LTCC (Low Temperature Co-fired Ceramics) microwave ceramic material with low cost, low dielectric constant and low loss and preparation method thereof |
| CN108249902B (en) * | 2018-02-06 | 2020-06-02 | 华中科技大学 | Silicate-based low-dielectric microwave dielectric ceramic and preparation method thereof |
| CN111763082B (en) * | 2019-04-01 | 2021-08-31 | 中国科学院上海硅酸盐研究所 | Barium strontium titanate-based dielectric ceramic material and preparation method and application thereof |
| CN115947587B (en) * | 2022-09-30 | 2024-02-02 | 郴州功田电子陶瓷技术有限公司 | Microwave dielectric ceramic and preparation method thereof |
| CN115925401B (en) * | 2022-11-10 | 2023-07-25 | 华中科技大学 | Low-dielectric silicate microwave dielectric ceramic material and preparation method thereof |
| CN117486609B (en) * | 2024-01-02 | 2024-04-12 | 中国科学院上海硅酸盐研究所 | Single-phase composite perovskite ceramic powder, microwave dielectric ceramic material and preparation method thereof |
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| CN1699275A (en) * | 2005-05-13 | 2005-11-23 | 中国科学院上海硅酸盐研究所 | Barium strontium titanate base electro-optical composite material and preparation method thereof |
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