CN101486569B - Low temperature sintering microwave ceramic material and preparation thereof - Google Patents

Low temperature sintering microwave ceramic material and preparation thereof Download PDF

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CN101486569B
CN101486569B CN2009100465883A CN200910046588A CN101486569B CN 101486569 B CN101486569 B CN 101486569B CN 2009100465883 A CN2009100465883 A CN 2009100465883A CN 200910046588 A CN200910046588 A CN 200910046588A CN 101486569 B CN101486569 B CN 101486569B
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temperature sintering
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CN101486569A (en
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翟继卫
姜海涛
沈波
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Tongji University
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Abstract

The invention belongs to the field of electronic material and apparatus, in particular relates to a low-temperature sintering microwave ceramics material and a preparation method thereof. The low-temperature sintering microwave ceramics material comprises components with the following molar percentage: 90.0 percent to 99.5 percent of Ba(1-x)SrxTiO3(x is equal to 0.2 to 0.7) as well as 0.5 percent to 10.0 percent of BaCu(B2O5). The invention develops a BST-BCB double-phase composite microwave ceramics material which has the advantages of dielectric constant seriation, low dielectric loss (high Q value) and higher modulation rate under a microwave frequency band and can be used on an adjustable microwave apparatus by carrying out composition to a microwave medium material BCB and a BST ferroelectric material.

Description

Low temperature sintering microwave ceramic material and preparation method thereof
Technical field
The invention belongs to electronic material and device technology field, be specifically related to a kind of low temperature sintering microwave ceramic material and preparation method thereof.
Background technology
In recent years; Ferroelectric ceramic(s) relies on its superior ferroelectric, piezoelectricity, pyroelectricity, electric light, light is sold off and performance such as nonlinear optics, is used to make devices such as ferroelectric storage memory, pyroelectric detector array, piezo-electric motor, ferroelectric ceramic capacitor, ferroelectric sensor, ferroelectric transducer array, ferroelectric microwave device, ferroelectric optical and integrated optics.Can be widely used in numerous areas such as microtronics, integrated optics, micromechanics.Developing along with ferroelectric ceramic(s) development of technology and Application Areas; Make the many functions such as ferroelectric, piezoelectricity, pyroelectricity, electric light, nonlinear optics of development research collection semi-conductor large-scale integrated circuit and ferroelectric multilayer ceramic and multifunctional circuit, device and the system of one; Have more tempting prospect, ferroelectric material has been described as microelectronic material of new generation.
The adjustable dielectric materials of microwave has wide application background on the adjustable components and parts of microwave, like the shifter on the phased array antenna, resonator, wave filter etc.With regard to research system, mainly concentrate on uhligite phase ferroelectric material at present, like strontium-barium titanate (BST) and doped series thereof.
Along with the miniaturized of modern device development and integrated; Multilayer material has shown its distinctive meliority, thereby the research of low temperature co-fired material has obtained suitable attention. and same, the research of BST pottery begins already; But; Its sintering temperature also reach expected value far away, so low fever's problem needs to be resolved hurrily all more than 1350 ℃.
As microwave dielectric material, in order in the adjustable microwave device, to obtain better application, material should have the higher figure of merit (ratio of tunable performance and dielectric loss).Thereby dielectric materials should have following performance: under microwave frequency, on the one hand, specific inductivity is low, and defective will be lacked, and dielectric loss and leakage current are low; On the other hand, under the DC biasing electric field, it is big that the variation of specific inductivity is wanted, and higher tunable performance is arranged. therefore, when reducing sintering temperature, also to keep more excellent dielectric properties.
The approach that reduces sintering temperature generally has three kinds of methods: doping low fever auxiliary agent; Chemical process prepares highly active powder; Compound low fever's material. existing report is studied BST stupalith low fever, as:---obtained result highly significant, still, the starting stage is still stated in BST low fever's research.Wherein when doping low fever auxiliary agent was too much, dielectric loss was bigger than normal, and low excessively like content, sintering character is poor, and dielectric properties are unstable. and chemical process prepares powder, the technology trouble, cost is higher, and the utmost point is not easy to industrial production.Y.Lu and J.Jean. are through adding Li 2O-B 2O 3-SiO 2-CaO-Al 2O 3, reduced the sintering temperature of BST, but its tuning rate less than 8%.People such as Rhim add a small amount of B 2O 3Reduce its sintering temperature, but worked as B 2O 3Addition when surpassing 1.0wt%, its dielectric properties can worsen because of the generation of second phase.Generally speaking, the component proportions of sintering agent can influence the performance of dielectric adjustable microwave ceramic material, if the content of sintering agent is low excessively, in the sintering process, helps the burning effect not obvious, and if the too high levels of sintering agent, then dielectric properties are poor.
From can know the correlative study result to material in the past; Different low fever's auxiliary agents; Different dopings can produce bigger influence to the performance of associated materials; Thereby can have preferable dielectric properties and a microwave tunable performance low sintering in order to obtain, and should consider that exploitation seeks a kind of low fever's auxiliary agent, realize practicability in the hope of making low-temperature sintering BST material.
Summary of the invention
One of the object of the invention provides a kind of passing through at strontium-barium titanate (Ba (1-x)Sr xTiO 3BST is called for short in (x=0.2~0.7)) compound BaCu (B in the function ceramics 2O 5) (be called for short BCB) reduce the low temperature sintering microwave ceramic material of BST material sintering temperature.
Another object of the present invention provides the preparation method of above-mentioned low temperature sintering microwave ceramic material.
To achieve these goals, the technical scheme of the present invention's employing is following:
A kind of low temperature sintering microwave ceramic material is the basis in the total mole number of low temperature sintering microwave ceramic material, and each component and molar content thereof are:
Ba (1-x)Sr xTiO 3,x=0.2~0.7 90.0%~99.5%
BaCu(B 2O 5) 0.5%~10.0%。
Above-mentioned low temperature sintering microwave ceramic material, the preferred scheme of each component and molar percentage thereof is:
Ba (1-x)Sr xTiO 3,x=0.2~0.7 95.0%~99.0%
BaCu(B 2O 5) 1.0%~5.0%。
The mean particle size of said ceramic medium material is between 0.5~2.5 micron, is preferably 0.5~1.5 micron.
On the other hand, the invention provides a kind of method of preparation, this method may further comprise the steps:
1) the main burning synthesizing of piece:
With BaTiO 3With SrTiO 3Powder uses the wet ball-milling method to mix, and makes Ba after the pre-burning (1-x)Sr xTiO 3Solid solution structure;
2) low fever's auxiliary agent is synthetic:
Select BaCO for use 3, CuO, H 3BO 3Be main raw material, add zirconia ball and absolute ethyl alcohol or deionized water ball milling, it is subsequent use to obtain the BCB powder after discharging oven dry pre-burning is ground;
3) mix after adding low fever's agent by mass ratio main burn in the piece, and the ball milling refinement, can make low temperature sintering microwave ceramic material.
Preferably, the main synthesis mode that burns piece is in the said step 1): with BaTiO 3With SrTiO 3Example is mixed in molar ratio, and the weight ratio 1~2: 1 of pressing deionized water and compound then adds deionized water, and the wet ball-milling method is mixed 24~36h, and oven dry places in the crucible, makes Ba after the pre-burning (1-x)Sr xTiO 3Solid solution structure.
Preferably, the synthesis mode of low fever's auxiliary agent is said step 2): select BaCO for use 3, CuO, H 3BO 3Being main raw material, is BaCO according to mol ratio 3, CuO and H 3BO 3Mol ratio be 1: 1: 2 proportion ingredient, confected materials is placed nylon ball grinder, add zirconia ball and absolute ethyl alcohol or deionized water, ball milling 20-24 hour, obtain the BCB powder after the discharging oven dry pre-burning grinding.
Calcined temperature in the said step 1) is 1000~1300 ℃.
The pre-burning time in the said step 1) is 0.5~15 hour, is preferably 2~8 hours.
Said step 2) calcined temperature in is 500~1050 ℃, is preferably 700~900 ℃.
Said step 2) the pre-burning time in is 0.5-15 hour, is preferably 1-5 hour.
Beneficial effect of the present invention:
The present invention adopts traditional electronic ceramic technology; Through carrying out microwave dielectric material BCB and BST ferroelectric material compound; Development obtains having the specific inductivity seriation under a kind of microwave frequency band, low-dielectric loss (high Q value), higher modulation rate; Can be used for the BST-BCB two-phase composite microwave ceramic material of adjustable microwave device, it has following principal feature:
(1) through the variation of control BST, BCB two phase plural components content, the specific inductivity of composite ceramic material can be adjustable continuously between 500~4000, can obtain the material system of specific inductivity seriation, widened the range of application of material;
(2) under the applying direct current electric field effect, said composite microwave ceramic material has higher dielectric tunable characteristic (>=43%), and under microwave frequency band, has higher Q value (>=146);
(3) sintering temperature is low, and the variation through BST, BCB two phase plural components content can obtain the low fever material system of sintering temperature between 860~950 ℃.Reduced the sintering temperature of dielectric material with adjustable significantly.Thereby can with electrode matching co-firing in silver (Ag)-palladium (Pd) alloy of full silver or low palladium content, and can greatly reduce the production cost of LTCC (LTCC).
BST of the present invention and the adjustable composite ceramic material of BCB dielectric not only have the adjustable rate of high dielectric of BST, and because the doping of low fever's microwave ceramic material also has lower sintering temperature, low-dielectric loss, the excellent specific property of high modulation.This preparing method's technology is simple, and cost is low, and material system not leaded (Pb), arsenic (As), cadmium harmful elements such as (Cd) have satisfied environmental protection requirement, and excellent performance is applicable to the exploitation and the design of adjustable microwave device.Simultaneously since the present invention to have chosen new low fever's microwave material and BST compound, confirmed new compositing formula; Reduced the sintering temperature of BST; Its sintering temperature is reduced to below 900 degree, and each item dielectric properties of this low fever's BST material are not all worsened, and especially have more excellent microwave property; It is under~1GHz frequency, and its Q can reach 146.
Description of drawings
The XRD spectra of the low-temperature sintering dielectric adjustable microwave composite ceramics of numbering 1 preparation among Fig. 1 embodiment 1.
Numbering 3 is to the XRD spectra of the low-temperature sintering dielectric adjustable microwave composite ceramics of numbering 7 preparations among Fig. 2 embodiment 1.
Numbering 4 is to the microscopic appearance figure of the low-temperature sintering dielectric adjustable microwave composite ceramics of numbering 7 preparations at 900 ℃/2h sintered sample among Fig. 3 embodiment 1
Numbering 3 is to the relation curve of low-temperature sintering dielectric adjustable microwave composite ceramics specific inductivity, loss and the temperature of numbering 7 preparations among Fig. 4 embodiment 1.
Numbering 3 is to the low-temperature sintering dielectric adjustable microwave composite ceramics specific inductivity of numbering 7 preparations and the relation curve of external dc field intensity among Fig. 5 embodiment 1.
Embodiment
Further specify the present invention below in conjunction with embodiment, but the present invention is not limited to these concrete real-time modes; Any change or improvement on basis of the present invention all belongs to protection scope of the present invention.
The preparation method of BST-BCB low-temperature sintering dielectric adjustable microwave composite ceramics provided by the present invention specifically comprises the steps:
(1) low fever's auxiliary agent B CB powder can adopt traditional electronic ceramic powder preparation method and solid reaction process to prepare: to select BaCO for use 3(99.99%), CuO (98%), H 3BO 3(99.5%) (its raw material is Chemical Reagent Co., Ltd., Sinopharm Group and provides) is main raw material; According to the molar ratio ingredient in the molecular formula; Confected materials is placed nylon ball grinder, added zirconia ball and absolute ethyl alcohol or deionized water ball milling 20-24 hour, the discharging oven dry afterwards 500 ℃~1050 ℃ pre-burning 0.5-15 hour; More preferably 700 ℃~900 ℃ pre-burning 1-5 hour, it is subsequent use to obtain the BCB powder after pre-burning is ground.
(2) adopt high-purity BaTiO 3, SrTiO 3, major ingredient to be mixed, the weight ratio 1: 1~2 of pressing compound and deionized water adds deionized water, and the wet ball-milling method is mixed 24~36h, and oven dry places in the crucible, pre-burning 0.5~15h under 1000~1300 ℃ condition, optimization time is 2~8h.Its final structure is Ba 1-xSr xTiO 3Solid solution structure.Ball milling is 20~24 hours once more, grinds to form powder through 110~300 ℃ of oven dry after the discharging, crosses 100~200 mesh sieves and obtains the BST material.
(3) take by weighing BST powder, BCB powder respectively according to aforementioned proportioning; Mix being placed in the ball grinder, add zirconia ball and absolute ethyl alcohol or water, ball milling 20~24 hours; Grind to form powder through 110-300 ℃ of oven dry after the discharging, cross the 100-200 mesh sieve and promptly get composite microwave ceramic material.
(4) Z 150PH (PVA) of employing 8~10% carries out granulation as sticker to above-mentioned composite powder, under 10~100MPa pressure, is pressed into the ceramic green sheet of desired size size through the forming mould of different model.
(5) the ceramic green sheet through 550 ℃~600 ℃ row is sticking handle after, the ceramic plate that obtains is carried out 860 ℃~950 ℃ (being incubated 2~4 hours) sintering processes, can obtain said composite microwave ceramic material.
Among the embodiment, the mass ratio of zirconia ball and ball milling material is preferably 1.0~1.5: 1; The mass ratio of absolute ethyl alcohol or deionized water and ball milling material is preferably 0.5~2.0: 1.
Embodiment 1
1, the preparation of BST:
With Ba 0.40Sr 0.60TiO 3Be example.Adopt high-purity BaTiO 3, SrTiO 3, major ingredient to be mixed, the weight ratio of pressing compound and deionized water adds deionized water at 1: 1, and the wet ball-milling method is mixed 24h, and oven dry places in the crucible, pre-burning 2h under 1000 ℃ condition, obtaining final structure is Ba 0.40Sr 0.60TiO 3Ball milling 24h grinds to form powder through 110 ℃ of oven dry after the discharging once more, crosses 200 mesh sieves, obtains the BST material.
2, the preparation of BCB:
Prepare burden according to certain mol proportion according to molecular formula respectively, take by weighing BaCO 3, CuO, H 3BO 3Be main raw material, confected materials is placed nylon ball grinder, added zirconia ball and absolute ethyl alcohol or deionized water ball milling 20 hours, discharging oven dry back obtains BCB 900 ℃ of pre-burnings 5 hours after the grinding.XRD spectra according to BCB shows, obtains the pure phase of BCB with this understanding.As shown in Figure 1.
3, preparation BST-BCB low-temperature sintering dielectric adjustable microwave composite ceramic material:
Table 1
Figure G2009100465883D00051
Figure G2009100465883D00061
Get BST, BCB powder according to set of dispense score another name in table 1 prescription.The compound of each prescription among the embodiment is put into nylon ball grinder, added zirconia ball and absolute ethyl alcohol ball milling 24 hours, discharging oven dry back powder is crossed 200 mesh sieves, promptly makes low temperature sintering microwave ceramic material.
According to traditional electronic ceramic technology; The Z 150PH (PVA) of employing 8% carries out granulation as sticker; Under 10MPa pressure; Dry method is pressed into diameter
Figure G2009100465883D00062
green sheet and
Figure G2009100465883D00063
h=5mm; The right cylinder of
Figure G2009100465883D00064
h=7mm,
Figure G2009100465883D00065
h=9mm,
Figure G2009100465883D00066
h=12mm; After the sticking processing of 550 ℃ rows; Sample is under air atmosphere; Sintering temperature is 900 ℃; Be incubated after 2 hours, obtain BST-BCB two phase composite ceramics samples.
4, phase structure, surface topography and the density measurement of BST-BCB low-temperature sintering dielectric adjustable microwave composite ceramics:
Above-mentioned numbering a~made ceramics sample of e prescription is utilized the XRD analysis phase structure, as shown in Figure 2.Utilize the scanning electron microscope analysis surface topography, as shown in Figure 3 being is numbered the ceramics sample of b, c, d, e.Utilize the density of Archimedes's method specimen, see table 1.
5, the dielectric properties of BST-BCB low-temperature sintering dielectric adjustable microwave composite ceramics test:
Above-mentioned numbering a is arrived the made ceramics sample polishing both surfaces of numbering e prescription; By silver, carried out the dielectric properties test behind the silver ink firing, numbering a to the prescription of numbering e made the relation curve of specific inductivity and loss and temperature of dielectric adjustable microwave medium material as shown in Figure 4; Numbering a to numbering e made the relation curve of specific inductivity and external dc field intensity of dielectric adjustable microwave medium material as shown in Figure 5.A among the figure, b, c, d, e represent the ceramics sample of numbering a to numbering e respectively.
6, the test of the microwave dielectric property of BST-BCB low-temperature sintering dielectric adjustable microwave composite ceramics:
With the right cylinder sample ceramics sample polishing both surfaces after firing, test No. a is as shown in table 2 to the microwave dielectric property of the prescription of numbering e.
Table 2
Figure G2009100465883D00067
Figure G2009100465883D00071
Show that by density in figure three stereoscan photographs and the table 2 compound a small amount of BCB can reduce the sintering temperature of BST, satisfies LTCC industrial production demand.Can find out that from Fig. 4 dielectric temperature spectral curve and table 2 dielectric constant of such composite microwave ceramic material can effectively be regulated by the variation of control BST, BCB two-phase compounding ingredients content, and can obtain the composite of low-dielectric loss, higher figure of merit Q.Can find out that through Fig. 5 such composite microwave ceramic material shows higher dielectric adjustable (T >=40%) at ambient temperature and is fit to designing and developing of adjustable microwave device (shifter etc.).
Embodiment 2
1, the preparation of BST:
With Ba 0.40Sr 0.60TiO 3Be example.Adopt high-purity BaTiO 3, SrTiO 3, major ingredient to be mixed, the weight ratio of pressing compound and deionized water adds deionized water at 1: 2, and the wet ball-milling method is mixed 24h, and oven dry places in the crucible, pre-burning 8h under 1300 ℃ condition, obtaining final structure is Ba 0.40Sr 0.60TiO 3Ball milling 24h grinds to form powder through 300 ℃ of oven dry after the discharging once more, crosses 100 mesh sieves, obtains the BST material.
2, the preparation of BCB:
Prepare burden according to certain mol proportion according to molecular formula respectively, take by weighing BaCO 3, CuO, H 3BO 3Be main raw material, confected materials is placed nylon ball grinder, added zirconia ball and absolute ethyl alcohol or de-ionized water polo 20 hours, discharging oven dry back obtains BCB 700 ℃ of pre-burnings 0.5 hour after the grinding.XRD spectra according to BCB shows, obtains the pure phase of BCB with this understanding.As shown in Figure 1.
3, preparation BST-BCB low-temperature sintering dielectric adjustable microwave composite ceramic material:
Method with reference to embodiment 1 prepares BST-BCB low-temperature sintering dielectric adjustable microwave composite ceramic material.
Embodiment 3
1, the preparation of BST:
With Ba 0.30Sr 0.70TiO 3Be example.Adopt high-purity BaTiO 3, SrTiO 3, major ingredient to be mixed, the weight ratio of pressing compound and deionized water adds deionized water at 1: 2, and the wet ball-milling method is mixed 24h, and oven dry places in the crucible, pre-burning 2h under 1000 ℃ condition, obtaining final structure is Ba 0.30Sr 0.70TiO 3Ball milling 24h grinds to form powder through 110 ℃ of oven dry after the discharging once more, crosses 200 mesh sieves, obtains the BST material.
2, the preparation of BCB:
Prepare burden according to certain mol proportion according to molecular formula respectively, take by weighing BaCO 3, CuO, H 3BO 3Be main raw material, confected materials is placed nylon ball grinder, added zirconia ball and absolute ethyl alcohol or deionized water ball milling 20-24 hour, discharging oven dry back obtains BCB 900 ℃ of pre-burnings 5 hours after the grinding.XRD spectra according to BCB shows, obtains the pure phase of BCB with this understanding.As shown in Figure 1.
3, preparation BST-BCB low-temperature sintering dielectric adjustable microwave composite ceramic material:
Table 1
Figure G2009100465883D00081
Get BST, BCB powder according to set of dispense score another name in table 1 prescription.The compound of each prescription among the embodiment is put into nylon ball grinder, added zirconia ball and absolute ethyl alcohol ball milling 24 hours, discharging oven dry back powder is crossed 200 mesh sieves, promptly makes low temperature sintering microwave ceramic material.
Embodiment 4
1, the preparation of BST:
With Ba 0.80Sr 0.20TiO 3Be example.Adopt high-purity BaTiO 3, SrTiO 3, major ingredient to be mixed, the weight ratio of pressing compound and deionized water adds deionized water at 1: 1, and the wet ball-milling method is mixed 24h, and oven dry places in the crucible, pre-burning 2h under 1000 ℃ condition, obtaining final structure is Ba 0.80Sr 0.20TiO 3Ball milling 24h grinds to form powder through 110 ℃ of oven dry after the discharging once more, crosses 200 mesh sieves, obtains the BST material.
2, the preparation of BCB:
Prepare burden according to certain mol proportion according to molecular formula respectively, take by weighing BaCO 3, CuO, H 3BO 3Be main raw material, confected materials is placed nylon ball grinder, added zirconia ball and absolute ethyl alcohol or deionized water ball milling 20-24 hour, discharging oven dry back obtains BCB 900 ℃ of pre-burnings 5 hours after the grinding.XRD spectra according to BCB shows, obtains the pure phase of BCB with this understanding.As shown in Figure 1.
3, preparation BST-BCB low-temperature sintering dielectric adjustable microwave composite ceramics:
Table 1
Get BST, BCB powder according to set of dispense score another name in table 1 prescription.The compound of each prescription among the embodiment is put into nylon ball grinder, added zirconia ball and absolute ethyl alcohol ball milling 24 hours, discharging oven dry back powder is crossed 200 mesh sieves, promptly makes low temperature sintering microwave ceramic material.

Claims (8)

1. a low temperature sintering microwave ceramic material is characterized in that, each component and molar percentage thereof are:
Ba (1-x)Sr xTiO 3,x=0.2~0.7 95.0%~99.0%
BaCu(B 2O 5) 1.0%~5.0%。
2. the preparation method of the described low temperature sintering microwave ceramic material of claim 1, its step is following:
1) the main burning synthesizing of piece:
With BaTiO 3With SrTiO 3Powder uses the wet ball-milling method to mix, and makes Ba after the pre-burning (1-x)Sr xTiO 3Solid solution structure;
2) low fever's auxiliary agent is synthetic:
Select BaCO for use 3, CuO, H 3BO 3Be main raw material, add zirconia ball and absolute ethyl alcohol or deionized water ball milling, it is subsequent use to obtain the BCB powder after discharging oven dry pre-burning is ground;
3) mix after adding low fever's agent by mass ratio main burn in the piece, and the ball milling refinement, can make low temperature sintering microwave ceramic material.
3. the preparation method of low temperature sintering microwave ceramic material as claimed in claim 2 is characterized in that, the main synthesis mode that burns piece is in the said step 1): with BaTiO 3With SrTiO 3Example is mixed in molar ratio, and the weight ratio 1~2: 1 of pressing deionized water and compound then adds deionized water, and the wet ball-milling method is mixed 24~36h, and oven dry places in the crucible, makes Ba after the pre-burning (1-x)Sr xTiO 3Solid solution structure.
4. the preparation method of low temperature sintering microwave ceramic material as claimed in claim 2 is characterized in that, said step 2) in the synthesis mode of low fever's auxiliary agent be: select BaCO for use 3, CuO, H 3BO 3Being main raw material, is BaCO according to mol ratio 3, CuO and H 3The X mol ratio of BO is 1: 1: 2 a proportion ingredient, and confected materials is placed nylon ball grinder, adds zirconia ball and absolute ethyl alcohol or deionized water, ball milling 20-24 hour, obtains the BCB powder after discharging oven dry pre-burning is ground.
5. the preparation method of low temperature sintering microwave ceramic material as claimed in claim 2 is characterized in that, the calcined temperature in the said step 1) is 1000~1300 ℃.
6. the preparation method of low temperature sintering microwave ceramic material as claimed in claim 2 is characterized in that, the pre-burning time in the said step 1) is 0.5~15 hour.
7. the preparation method of low temperature sintering microwave ceramic material as claimed in claim 2 is characterized in that, said step 2) in calcined temperature be 500~1050 ℃.
8. the preparation method of low temperature sintering microwave ceramic material as claimed in claim 2 is characterized in that, said step 2) in the pre-burning time be 0.5-15 hour.
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CN101671169B (en) * 2009-09-19 2012-05-23 桂林理工大学 Low temperature sintering microwave medium ceramic material and preparation method thereof
CN103396117A (en) * 2013-08-01 2013-11-20 天津大学 Low-temperature sintered strontium titanate energy-storing medium ceramic material and preparation method thereof
CN106316348B (en) * 2016-08-16 2019-04-02 贵州玉屏迈威科技有限公司 A kind of nano ceramic microwave aqueous synthesis method
CN106278192B (en) * 2016-08-24 2019-03-19 河南科技大学 A kind of preparation method of the multi-phase microwave dielectric ceramic with jujube cake model structure
CN106587991B (en) * 2016-12-06 2020-02-18 电子科技大学 Low-temperature sintered composite microwave dielectric ceramic material and preparation method thereof
CN110256088A (en) * 2019-06-14 2019-09-20 山东格仑特电动科技有限公司 A kind of microwave-medium ceramics composite sintering agent and preparation method thereof

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