CN101486569A - Low temperature sintering microwave ceramic material and preparation thereof - Google Patents
Low temperature sintering microwave ceramic material and preparation thereof Download PDFInfo
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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
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 multifunctional circuit, device and the system of all multi-functional and one of ferroelectric, the piezoelectricity, pyroelectricity, electric light, nonlinear optics etc. of development research collection semi-conductor large-scale integrated circuit and ferroelectric multilayer ceramic, 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, as the phase shifter on the phased array antenna, resonator, wave filter etc.With regard to research system, mainly concentrate on uhligite phase ferroelectric material at present, as strontium-barium titanate (BST) and doped series thereof.
Along with the miniaturization of modern device development and integrated, multilayer material has shown its distinctive superiority, thereby the research of low temperature co-fired material has obtained suitable attention. 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 to obtain better application in the adjustable microwave device, 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 direct-current 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 as content, sintering character is poor, the dielectric properties instability. 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 by 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, sintering aids role is 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, should consider a kind of low fever's auxiliary agent of exploitation searching, realize practicability in the hope of making low-temperature sintering BST material.
Summary of the invention
One of purpose of the present invention provides a kind of passing through at strontium-barium titanate (Ba
(1-x)Sr
xTiO
3(x=0.2～0.7) is called for short BST) 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 solution used in the present invention is as follows:
A kind of low temperature sintering microwave ceramic material, based on the total mole number of low temperature sintering microwave ceramic material, 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 described 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 dehydrated alcohol or deionized water ball milling, it is standby 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 described step 1): with BaTiO
3With SrTiO
3Example is mixed in molar ratio, and the weight ratio 1～2:1 that presses 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 described 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 the proportion ingredient of 1:1:2, confected materials is placed nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water, ball milling 20-24 hour, obtain the BCB powder after discharging oven dry pre-burning is ground.
Calcined temperature in the described step 1) is 1000～1300 ℃.
The pre-burning time in the described step 1) is 0.5～15 hour, is preferably 2～8 hours.
Described step 2) calcined temperature in is 500～1050 ℃, is preferably 700～900 ℃.
Described 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, by 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) by 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, described composite microwave ceramic material has higher dielectric tunable characteristic (〉=43%), and has higher Q value (〉=146) under microwave frequency band;
(3) sintering temperature is low, and the variation by 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 preparation 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, because it is compound that the present invention has chosen new low fever's microwave material and BST, determined new compositing formula, reduced the sintering temperature of BST, its sintering temperature is reduced to below 900 degree, and every 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 dehydrated alcohol or deionized water ball milling 20-24 hour, discharging oven dry back 500 ℃～1050 ℃ pre-burning 0.5-15 hour, more preferably 700 ℃～900 ℃ pre-burning 1-5 hour, it is standby to obtain the BCB powder after pre-burning is ground.
(2) adopt high-purity BaTiO
3, SrTiO
3, major ingredient to be mixed, weight ratio 1:1～2 of pressing compound and deionized water add 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, the 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 dehydrated 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) polyvinyl alcohol (PVA) of employing 8～10% carries out granulation as binding agent to above-mentioned composite powder, under 10～100MPa pressure, is pressed into the ceramic green sheet of desired size size by 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 described 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 dehydrated 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 is mixed, the weight ratio 1:1 that presses compound and deionized water adds deionized water, 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 dehydrated 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 BCB pure phase with this understanding.As shown in Figure 1.
3, preparation BST-BCB low-temperature sintering dielectric adjustable microwave composite ceramic material:
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 dehydrated 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 polyvinyl alcohol (PVA) of employing 8% carries out granulation as binding agent, and under 10MPa pressure, dry method is pressed into diameter
=10mm green sheet and
=10mm, h=5mm,
=15mm, h=7mm,
=18mm, h=9mm,
The right cylinder of=25mm, h=12mm, after the sticking processing of 550 ℃ rows, sample is under air atmosphere, and sintering temperature is 900 ℃, is incubated after 2 hours, obtains BST-BCB two-phase composite ceramics sample.
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 be the ceramics sample that is numbered 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 specific inductivity of dielectric adjustable microwave medium material and the relation curve of loss and temperature as shown in Figure 4; Numbering a to numbering e made the specific inductivity of dielectric adjustable microwave medium material and the relation curve of external dc field intensity 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
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.From Fig. 4 dielectric temperature spectral curve and table 2 as can be seen, the specific inductivity of such composite microwave ceramic material can effectively be regulated by the variation of control BST, BCB two-phase plural components content, and can obtain the matrix material of low-dielectric loss, higher figure of merit Q.As seen in Figure 5, such composite microwave ceramic material shows designing and developing of higher dielectric adjustable (T 〉=40%) suitable adjustable microwave device (phase shifter etc.) at ambient temperature.
Embodiment 2
1, the preparation of BST:
With Ba
0.40Sr
0.60TiO
3Be example.Adopt high-purity BaTiO
3, SrTiO
3, major ingredient is mixed, the weight ratio 1:2 that presses compound and deionized water adds deionized water, 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 dehydrated alcohol or deionization 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 BCB pure phase 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 is mixed, the weight ratio 1:2 that presses compound and deionized water adds deionized water, 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 dehydrated 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 BCB pure phase with this understanding.As shown in Figure 1.
3, preparation BST-BCB low-temperature sintering dielectric adjustable microwave composite ceramic material:
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 dehydrated 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 is mixed, the weight ratio 1:1 that presses compound and deionized water adds deionized water, 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 dehydrated 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 BCB pure phase 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 dehydrated alcohol ball milling 24 hours, discharging oven dry back powder is crossed 200 mesh sieves, promptly makes low temperature sintering microwave ceramic material.
Claims (9)
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 90.0％～99.5％
BaCu(B
2O
5) 0.5％～10.0％。
2, low temperature sintering microwave ceramic material as claimed in claim 1 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％。
3, the preparation method of claim 1 or 2 described low temperature sintering microwave ceramic materials, its step is as follows:
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 dehydrated alcohol or deionized water ball milling, it is standby 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.
4, the preparation method of low temperature sintering microwave ceramic material as claimed in claim 3 is characterized in that, the main synthesis mode that burns piece is in the described step 1): with BaTiO
3With SrTiO
3Example is mixed in molar ratio, and the weight ratio 1～2:1 that presses 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.
5, the preparation method of low temperature sintering microwave ceramic material as claimed in claim 3 is characterized in that, described 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
3BO
3Mol ratio be the proportion ingredient of 1:1:2, confected materials is placed nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water, ball milling 20-24 hour, obtain the BCB powder after discharging oven dry pre-burning is ground.
6, the preparation method of low temperature sintering microwave ceramic material as claimed in claim 3 is characterized in that, the calcined temperature in the described step 1) is 1000～1300 ℃.
7, the preparation method of low temperature sintering microwave ceramic material as claimed in claim 3 is characterized in that, the pre-burning time in the described step 1) is 0.5～15 hour.
8, the preparation method of low temperature sintering microwave ceramic material as claimed in claim 3 is characterized in that, described step 2) in calcined temperature be 500～1050 ℃.
9, the preparation method of low temperature sintering microwave ceramic material as claimed in claim 3 is characterized in that, described 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 |
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| CN100434392C (en) * | 2007-01-18 | 2008-11-19 | 同济大学 | Ba1-xSrxTiO3-Mg2TiO4 two-phase composite ceramic material and its preparing process |
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| CN106316348A (en) * | 2016-08-16 | 2017-01-11 | 贵州玉屏迈威科技有限公司 | Nanoscale ceramic-material microwave aqueous-phase synthesis method |
| CN106278192A (en) * | 2016-08-24 | 2017-01-04 | 河南科技大学 | A kind of multi-phase microwave dielectric ceramic with Fructus Jujubae cake model structure and preparation method thereof |
| 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 |
| CN106587991A (en) * | 2016-12-06 | 2017-04-26 | 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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