CN102976751B - Low-temperature sintering microwave dielectric ceramic material and preparation method thereof - Google Patents
Low-temperature sintering microwave dielectric ceramic material and preparation method thereof Download PDFInfo
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- CN102976751B CN102976751B CN201210478550.5A CN201210478550A CN102976751B CN 102976751 B CN102976751 B CN 102976751B CN 201210478550 A CN201210478550 A CN 201210478550A CN 102976751 B CN102976751 B CN 102976751B
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000009766 low-temperature sintering Methods 0.000 title abstract description 9
- 239000000919 ceramic Substances 0.000 claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 239000011230 binding agent Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims description 99
- 239000000843 powder Substances 0.000 claims description 62
- 238000009413 insulation Methods 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 36
- 239000011812 mixed powder Substances 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 238000007493 shaping process Methods 0.000 claims description 9
- 239000007767 bonding agent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 14
- 229910052788 barium Inorganic materials 0.000 abstract description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 abstract 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 abstract 2
- 229920002689 polyvinyl acetate Polymers 0.000 abstract 2
- 239000011118 polyvinyl acetate Substances 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 239000010955 niobium Substances 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 6
- 150000001553 barium compounds Chemical class 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a low-temperature sintering microwave dielectric ceramic material and a preparation method thereof. The low-temperature sintering microwave dielectric ceramic material comprises ywt%[(1-x)Ba5Nb4O15-xBaNb2O6]+zwt%A, wherein A is a product of reaction between CuO and HBO3; x=0.1-0.3; 0<z<20; and y+z=100. According to the invention, A is obtained by the reaction between CuO and HBO3; the product is insoluble in solvents such as water, ethanol and the like and does not generate a gelling reaction with binders such as PVA (polyvinyl acetate), PVB (polyvinyl butyral) and the like, thus the requirements of the LTCC (low temperature co-fired ceramic) technology are met, and a high-density ceramic membrane can be obtained; the problem of the reaction with the barium element in the Ba5Nb4O15 ceramic is avoided so that the content of the BaNb2O6 phase is accurately controlled; and the material has good adjustability of resonant frequency temperature coefficient, low dielectric loss and high material quality factor, and the sintering temperature is lower than 880 DEG C. According to the invention, rare earth elements are not involved, the raw materials are cheap, and the cost is relatively low, thus the material is suitable for industrial production of microwave dielectric ceramic devices.
Description
Technical field
The present invention relates to the microwave-medium ceramics technical field of the microwave devices such as microwave communication dielectric resonator, oscillator, be specifically related to a kind of low-temperature sintered microwave dielectric ceramic material and preparation method.
Background technology
Along with modern communication technology is to the active demand of the components and parts of miniaturized, integrated, modularization and low cost, LTCC (Low Temperature Co-fired Ceramics, the LTCC) technology with excellent electricity, machinery, hot property and high reliability has become the one preferred technique of communication components and parts manufacture.The maximum feature of LTCC technology is to adopt base metal (as Ag) as multilayer wiring conductor material, improves signal transmission rate and reliability, and multiple microwave electron components and parts can be embedded in sintering in substrate and improve packaging density at double.The components and parts adopting this technology to prepare have that dielectric loss is low, reliability is high, low cost and other advantages, have a wide range of applications.
Because the fusing point of metal A g electrode is at 960 DEG C, in order to realize with ceramic co-fired, LTCC technology requires that the sintering temperature of pottery is lower than 900 DEG C.Current great majority have the microwave-medium ceramics sintering temperature of excellent properties higher than 1200 DEG C, have the Ba of excellent microwave dielectric property
5nb
4o
15pottery is also like this.It is reported, Ba
5nb
4o
15the dielectric constant of microwave-medium ceramics is ε
r=41, quality factor q × f=57000GHz, temperature coefficient of resonance frequency τ
f=50ppm/ DEG C, but sintering temperature is higher than 1380 DEG C.Low temperature co-fired in order to what realize with Ag electrode, the people such as Kin.J.R are at " Journal of the American Society " 85 volumes " Microwave Dielectric Properties of Low-Fired Ba in 2002
5nb
4o
15" one the article pointed out and add low melting point oxide B at pottery
2o
3sintering temperature can be down to 900 DEG C, quality factor q × f=18700GHz, temperature coefficient of resonance frequency also can be made close to zero simultaneously.
But adopt such scheme to prepare LTCC and still there is more deficiency, be in particular in:
(1) due to B
2o
3soluble in water, ethanol equal solvent, and with the binding agent generation gelling reactions such as the most frequently used PVA, PVB, make ceramic powder can not obtain highdensity ceramic diaphragm after curtain coating.
(2), in technique scheme, the mechanism reducing sintering temperature is B
2o
3with Ba
5nb
4o
15in pottery, barium element reaction generates the low melting point oxide of barium, boron, oxygen system, but the oxide ester mp of all barium, boron, oxygen system is all greater than 890 DEG C, and this technology can not reduce sintering temperature further.Meanwhile, temperature coefficient of resonance frequency reduced be due to system barium element disappearance cause more than niobium element and a small amount of barium Element generation BaNb
2o
6phase, but due to barium, boron, oxygen system oxide huge number, BaNb
2o
6the actual content of phase is difficult to control, and in actual production, temperature coefficient of resonance frequency is difficult to control.
Therefore, need a kind of low-temperature sintered microwave dielectric ceramic material, the low melting point oxide in this material be water insoluble, ethanol equal solvent, and not with the binding agent generation gelling reactions such as PVA, PVB, to obtain highdensity ceramic diaphragm; Do not exist and Ba
5nb
4o
15in pottery, the problem of barium element reaction, makes BaNb
2o
6obtain content mutually precisely controlled, reduce sintering temperature further simultaneously; And there is lower cost, the industrialization being applicable to microwave-medium ceramics device is produced.
Summary of the invention
In view of this, the object of this invention is to provide a kind of low-temperature sintered microwave dielectric ceramic material and preparation method thereof, low melting point oxide in this material is water insoluble, ethanol equal solvent, and not with the binding agent generation gelling reactions such as PVA, PVB, to obtain highdensity ceramic diaphragm; Do not exist and Ba
5nb
4o
15in pottery, the problem of barium element reaction, makes BaNb
2o
6obtain content mutually precisely controlled, reduce sintering temperature further simultaneously; And there is lower cost, the industrialization being applicable to microwave-medium ceramics device is produced.
Low-temperature sintered microwave dielectric ceramic material of the present invention, comprising: ywt% [(1-x) Ba
5nb
4o
15-xBaNb
2o
6]+zwt%A, wherein: A is CuO and HBO
3reacted product; X=0.1 ~ 0.3,0<z<20, y+z=100.
Further, described A is CuO and HBO
3in mole than 1:(5 ~ 9) ratio at 1000 DEG C ~ 1200 DEG C, react the product after 1 ~ 4 hour;
Further, described A is CuB
8o
13;
Further, x=0.1 ~ 0.2,0<z<10.
The invention also discloses a kind of preparation method of low-temperature sintered microwave dielectric ceramic material, comprise the following steps:
A. Ba is prepared
5nb
4o
15ceramic powder;
B. BaNb is prepared
2o
6ceramic powder;
C.CuO and HBO
3reaction obtains product A;
D. ywt% [(1-x) Ba is pressed
5nb
4o
15-xBaNb
2o
6]+zwt%A, x=0.1 ~ 0.3,0<z<20, y+z=100 takes Ba
5nb
4o
15ceramic powder, BaNb
2o
6ceramic powder and product A also form mixed powder;
E. in the mixed powder of steps d, add binding agent and compressing after granulation, after sintering, form microwave dielectric ceramic materials.
Further, in step c, by CuO and HBO
3mole than for 1:(5 ~ 9) proportions, add in ball grinder and adopt dry type ball-milling method mixing and ball milling 2 ~ 6 hours, obtain product A 1000 DEG C ~ 1200 DEG C insulations after 1 ~ 4 hour and pulverize;
Further, in step a, by Ba
5nb
4o
15stoichiometric proportion take BaCO
3and Nb
2o
5raw material, adopts wet ball-milling method mixing and ball milling 20 ~ 24 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and within 1 ~ 6 hour, obtains Ba after drying in an oven 1000 DEG C ~ 1200 DEG C insulations
5nb
4o
15ceramic powder;
In step b, by BaNb
2o
6stoichiometric proportion take BaCO
3and Nb
2o
5raw material, the raw material taken is adopted wet ball-milling method mixing and ball milling 20 ~ 24 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, 1000 DEG C ~ 1200 DEG C insulations 1 ~ 4 hour after drying in an oven, cool to 900 DEG C ~ 950 DEG C insulations with the speed of 2 ~ 5 DEG C/min and obtain BaNb in 1 ~ 6 hour
2o
6ceramic powder;
In steps d, by ywt% [(1-x) Ba
5nb
4o
15-xBaNb
2o
6] formula of+zwt%A, x=0.1 ~ 0.3,0<z<20, y+z=100 takes the Ba of step a gained
5nb
4o
15the BaNb of ceramic powder, step b gained
2o
6the product A powder of ceramic powder and step c gained, adopts wet ball-milling method mixing and ball milling 22 ~ 24 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and dries in an oven and obtains mixed powder;
In step e, the addition of bonding agent is the 1wt% ~ 3.5wt% of mixed powder quality in steps d, obtains shaping raw stock after compressing at 500 DEG C ~ 600 DEG C insulations, 1 ~ 3 hour binder removal; Described raw stock is placed in muffle furnace and sinters, and obtains microwave dielectric ceramic materials.
Further, in step c, CuO and HBO
3mole than for 1:(6 ~ 8);
Further, in step e, described binding agent is polyvinyl alcohol water solution, and concentration is 1.0wt% ~ 5.0wt%;
Further, in step e, heating rate 1.5 ~ 6 DEG C/min of sintering process, sintering temperature is 830 ~ 880 DEG C, and temperature retention time is 1 ~ 4 hour at this temperature.
The invention has the beneficial effects as follows: low-temperature sintered microwave dielectric ceramic material of the present invention, low melting point oxide adopts CuO and HBO
3the product that reaction obtains, this product is water insoluble, ethanol equal solvent, and not with the binding agent generation gelling reaction such as PVA, PVB, meet LTCC technological requirement, highdensity ceramic diaphragm can be obtained; Do not exist and Ba
5nb
4o
15in pottery, the problem of barium element reaction, makes BaNb
2o
6obtain content mutually precisely controlled, there is good temperature coefficient of resonance frequency adjustability, low dielectric loss, high material quality factor, microwave dielectric ceramic materials dielectric constant 42< ε of the present invention
r<44, quality factor q × f>8000GHz, temperature coefficient of resonance frequency-7ppm/ DEG C of < τ
f<5ppm/ DEG C; Reduce sintering temperature further, sintering temperature is lower than 880 DEG C simultaneously; And the present invention does not relate to rare earth element, cost of material is cheap, has lower cost, and the industrialization being applicable to microwave-medium ceramics device is produced.
Embodiment
Low-temperature sintered microwave dielectric ceramic material of the present invention, comprising: ywt% [(1-x) Ba
5nb
4o
15-xBaNb
2o
6]+zwt%A, wherein: A is CuO and HBO
3reacted product; X=0.1 ~ 0.3,0<z<20, y+z=100; Wt% is weight percentage.
In the present embodiment, described A is CuO and HBO
3in mole than 1:(5 ~ 9) ratio at 1000 DEG C ~ 1200 DEG C, react the product after 1 ~ 4 hour.
In the present embodiment, described A is CuB
8o
13.
In the present embodiment, x=0.1 ~ 0.2,0<z<10.
The invention also discloses a kind of preparation method of low-temperature sintered microwave dielectric ceramic material, comprise the following steps:
A. Ba is prepared
5nb
4o
15ceramic powder;
B. BaNb is prepared
2o
6ceramic powder;
C.CuO and HBO
3reaction obtains product A;
D. ywt% [(1-x) Ba is pressed
5nb
4o
15-xBaNb
2o
6]+zwt%A, x=0.1 ~ 0.3,0<z<20, y+z=100 takes Ba
5nb
4o
15ceramic powder, BaNb
2o
6ceramic powder and product A also form mixed powder;
E. in the mixed powder of steps d, add binding agent and compressing after granulation, after sintering, form microwave dielectric ceramic materials.
In the present embodiment, in step c, by CuO and HBO
3mole than for 1:(5 ~ 9) proportions, add in ball grinder and adopt dry type ball-milling method mixing and ball milling 2 ~ 6 hours, obtain product A 1000 DEG C ~ 1200 DEG C insulations after 1 ~ 4 hour and pulverize;
In the present embodiment, in step a, by Ba
5nb
4o
15stoichiometric proportion take BaCO
3and Nb
2o
5raw material, adopts wet ball-milling method mixing and ball milling 20 ~ 24 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and within 1 ~ 6 hour, obtains Ba after drying in an oven 1000 DEG C ~ 1200 DEG C insulations
5nb
4o
15ceramic powder;
In step b, by BaNb
2o
6stoichiometric proportion take BaCO
3and Nb
2o
5raw material, the raw material taken is adopted wet ball-milling method mixing and ball milling 20 ~ 24 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, 1000 DEG C ~ 1200 DEG C insulations 1 ~ 4 hour after drying in an oven, cool to 900 DEG C ~ 950 DEG C insulations with the speed of 2 ~ 5 DEG C/min and obtain BaNb in 1 ~ 6 hour
2o
6ceramic powder;
In steps d, by ywt% [(1-x) Ba
5nb
4o
15-xBaNb
2o
6] formula of+zwt%A, x=0.1 ~ 0.3,0<z<20, y+z=100 takes the Ba of step a gained
5nb
4o
15the BaNb of ceramic powder, step b gained
2o
6the product A powder of ceramic powder and step c gained, adopts wet ball-milling method mixing and ball milling 22 ~ 24 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and dries in an oven and obtains mixed powder;
In step e, the addition of bonding agent is the 1wt% ~ 3.5wt% of mixed powder quality in steps d, obtains shaping raw stock after compressing at 500 DEG C ~ 600 DEG C insulations, 1 ~ 3 hour binder removal; Described raw stock is placed in muffle furnace and sinters, and obtains microwave dielectric ceramic materials.
In the present embodiment, in step c, CuO and HBO
3mole than for 1:(6 ~ 8);
In the present embodiment, in step e, described binding agent is polyvinyl alcohol water solution, and concentration is 1.0wt% ~ 5.0wt%;
In the present embodiment, in step e, heating rate 1.5 ~ 6 DEG C/min of sintering process, sintering temperature is 830 ~ 880 DEG C, and temperature retention time is 1 ~ 4 hour at this temperature.
Be embodiments of the invention below:
Embodiment one
Comprise: ywt% [(1-x) Ba
5nb
4o
15-xBaNb
2o
6]+zwt%A, wherein: A is CuO and HBO
3in mole than the ratio of 1:5.5 react at 1150 DEG C 1.5 little time after product; X=0.2, z=4, y=96.
The preparation method of the present embodiment low temperature sintering microwave dielectric ceramic materials, comprises the following steps:
A. Ba is prepared
5nb
4o
15ceramic powder:
By Ba
5nb
4o
15stoichiometric proportion take BaCO
3and Nb
2o
5raw material, adopts wet ball-milling method mixing and ball milling 20 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and within 6 hours, obtains Ba after drying in an oven 1200 DEG C of insulations
5nb
4o
15ceramic powder;
B. BaNb is prepared
2o
6ceramic powder:
By BaNb
2o
6stoichiometric proportion take BaCO
3and Nb
2o
5raw material, the raw material taken is adopted wet ball-milling method mixing and ball milling 24 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, 1200 DEG C of DEG C of insulations 4 hours after drying in an oven, cool to 950 DEG C of insulations with the speed of 2 DEG C/min and obtain BaNb in 4 hours
2o
6ceramic powder;
C.CuO and HBO
3reaction obtains product A:
By CuO and HBO
3mole than being the proportions of 1:5.5, add in ball grinder and adopt dry type ball-milling method mixing and ball milling 5 hours, obtain product A 1150 DEG C of insulations after 1.5 hours and pulverize;
D. Ba is taken
5nb
4o
15ceramic powder, BaNb
2o
6ceramic powder and product A also form mixed powder; The raw material taken is adopted wet ball-milling method mixing and ball milling 22 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, dries in an oven and obtain mixed powder;
E. in the mixed powder of steps d, binding agent is added and compressing after granulation, shaping raw stock is obtained at 500 DEG C of insulations, 1 hour binder removal, this life stock is placed in muffle furnace and is raised to 870 DEG C of insulations 3.5 hours with the speed of 5 DEG C/min from room temperature, after sintering, form microwave dielectric ceramic materials; The binding agent of the present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase of the ceramics sample after adopting x-ray diffractometer (XRD) analysis to sinter is Ba
5nb
4o
15phase and BaNb
2o
6phase two-phase, adopts Agilent H98722ET vector grid analyzer test result: DIELECTRIC CONSTANT ε
r=43.4, quality factor q × f=8910.9GHz, there are very high quality factor.Temperature coefficient of resonance frequency τ
f=-3ppm/ DEG C, meets real requirement.Compared with prior art, sintering temperature is reduced to 870 DEG C from 900 DEG C, avoids simultaneously and reacts with polyvinyl alcohol water solution, can have the ceramic diaphragm that preparation is finer and close; It also avoid and react with containing barium compound, temperature coefficient of resonance frequency-3ppm/ DEG C and more stable, meet LTCC technology needs.
Embodiment two
Comprise: ywt% [(1-x) Ba
5nb
4o
15-xBaNb
2o
6]+zwt%A, wherein: A is CuO and HBO
3in mole than the ratio of 1:8 react at 1100 DEG C 2 little time after product; X=0.15, z=10, y=90.
The preparation method of the present embodiment low temperature sintering microwave dielectric ceramic materials, comprises the following steps:
A. Ba is prepared
5nb
4o
15ceramic powder:
By Ba
5nb
4o
15stoichiometric proportion take BaCO
3and Nb
2o
5raw material, adopts wet ball-milling method mixing and ball milling 24 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and within 2 hours, obtains Ba after drying in an oven 1200 DEG C of insulations
5nb
4o
15ceramic powder;
B. BaNb is prepared
2o
6ceramic powder:
By BaNb
2o
6stoichiometric proportion take BaCO
3and Nb
2o
5raw material, the raw material taken is adopted wet ball-milling method mixing and ball milling 24 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, 1200 DEG C of DEG C of insulations 2 hours after drying in an oven, cool to 950 DEG C of insulations with the speed of 2 DEG C/min and obtain BaNb in 3 hours
2o
6ceramic powder;
C.CuO and HBO
3reaction obtains product A:
By CuO and HBO
3mole than being the proportions of 1:8, add in ball grinder and adopt dry type ball-milling method mixing and ball milling 5 hours, obtain product A 1100 DEG C of insulations after 2 hours and pulverize; In the present embodiment, CuO and HBO
3product is under these conditions CuB
8o
13;
D. Ba is taken
5nb
4o
15ceramic powder, BaNb
2o
6ceramic powder and product A also form mixed powder; The raw material taken is adopted wet ball-milling method mixing and ball milling 24 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, dries in an oven and obtain mixed powder;
E. in the mixed powder of steps d, binding agent is added and compressing after granulation, shaping raw stock is obtained at 600 DEG C of insulations, 2 hours binder removals, this life stock is placed in muffle furnace and is raised to 830 DEG C of insulations 3 hours with the speed of 5 DEG C/min from room temperature, after sintering, form microwave dielectric ceramic materials; The binding agent of the present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase of the ceramics sample after adopting x-ray diffractometer (XRD) analysis to sinter is Ba
5nb
4o
15phase and BaNb
2o
6phase two-phase.Adopt Agilent H98722ET vector grid analyzer test result: DIELECTRIC CONSTANT ε
r=42.5, quality factor q × f=13710.9GHz, there are very high quality factor; Temperature coefficient of resonance frequency τ
f=0ppm/ DEG C, compares with embodiment 1, and quality factor have had and comparatively significantly improve, and temperature coefficient of resonance frequency is zero; Compared with prior art, sintering temperature is reduced to 830 DEG C from 900 DEG C, avoids simultaneously and reacts with polyvinyl alcohol water solution, can have the ceramic diaphragm that preparation is finer and close; It also avoid and react with containing barium compound, better meet LTCC technology needs.
Embodiment three
Comprise: ywt% [(1-x) Ba
5nb
4o
15-xBaNb
2o
6]+zwt%A, wherein: A is CuO and HBO
3in mole than the ratio of 1:5 react at 1000 DEG C 4 little time after product; X=0.1, z=19.7, y=80.3.
The preparation method of the present embodiment low temperature sintering microwave dielectric ceramic materials, comprises the following steps:
A. Ba is prepared
5nb
4o
15ceramic powder:
By Ba
5nb
4o
15stoichiometric proportion take BaCO
3and Nb
2o
5raw material, adopts wet ball-milling method mixing and ball milling 22 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and within 6 hours, obtains Ba after drying in an oven 1000 DEG C of insulations
5nb
4o
15ceramic powder;
B. BaNb is prepared
2o
6ceramic powder:
By BaNb
2o
6stoichiometric proportion take BaCO
3and Nb
2o
5raw material, the raw material taken is adopted wet ball-milling method mixing and ball milling 20 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, 1000 DEG C of insulations 4 hours after drying in an oven, cool to 900 DEG C of insulations with the speed of 5 DEG C/min and obtain BaNb in 6 hours
2o
6ceramic powder;
C.CuO and HBO
3reaction obtains product A:
By CuO and HBO
3mole than being the proportions of 1:5, add in ball grinder and adopt dry type ball-milling method mixing and ball milling 2 hours, obtain product A 1000 DEG C of insulations after 4 hours and pulverize;
D. Ba is taken
5nb
4o
15ceramic powder, BaNb
2o
6ceramic powder and product A also form mixed powder; The raw material taken is adopted wet ball-milling method mixing and ball milling 22 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, dries in an oven and obtain mixed powder;
E. in the mixed powder of steps d, binding agent is added and compressing after granulation, shaping raw stock is obtained at 550 DEG C of insulations, 3 hours binder removals, this life stock is placed in muffle furnace and is raised to 830 DEG C of insulations 2 hours with the speed of 1.5 DEG C/min from room temperature, after sintering, form microwave dielectric ceramic materials; The binding agent of the present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase of the ceramics sample after adopting x-ray diffractometer (XRD) analysis to sinter is Ba
5nb
4o
15phase and BaNb
2o
6phase two-phase.Adopt Agilent H98722ET vector grid analyzer test result: DIELECTRIC CONSTANT ε
r=42.9, quality factor q × f=8321.5GHz, there are very high quality factor; Temperature coefficient of resonance frequency τ
f=5ppm/ DEG C, quality factor are low compared with embodiment 2; Compared with prior art, sintering temperature is reduced to 830 DEG C from 900 DEG C, avoids simultaneously and reacts with polyvinyl alcohol water solution, can have the ceramic diaphragm that preparation is finer and close; It also avoid and react with containing barium compound, LTCC technology needs can be met.
Embodiment four
Comprise: ywt% [(1-x) Ba
5nb
4o
15-xBaNb
2o
6]+zwt%A, wherein: A is CuO and HBO
3in mole than the ratio of 1:9 react at 1200 DEG C 1 little time after product; X=0.3, z=0.05, y=99.5.
The preparation method of the present embodiment low temperature sintering microwave dielectric ceramic materials, comprises the following steps:
A. Ba is prepared
5nb
4o
15ceramic powder:
By Ba
5nb
4o
15stoichiometric proportion take BaCO
3and Nb
2o
5raw material, adopts wet ball-milling method mixing and ball milling 24 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and within 2 hours, obtains Ba after drying in an oven 1100 DEG C of insulations
5nb
4o
15ceramic powder;
B. BaNb is prepared
2o
6ceramic powder:
By BaNb
2o
6stoichiometric proportion take BaCO
3and Nb
2o
5raw material, the raw material taken is adopted wet ball-milling method mixing and ball milling 22 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, 1100 DEG C of DEG C of insulations 3 hours after drying in an oven, cool to 925 DEG C of insulations with the speed of 3 DEG C/min and obtain BaNb in 4 hours
2o
6ceramic powder;
C.CuO and HBO
3reaction obtains product A:
By CuO and HBO
3mole than being the proportions of 1:9, add in ball grinder and adopt dry type ball-milling method mixing and ball milling 4 hours, obtain product A 1200 DEG C of insulations after 1 hour and pulverize;
D. Ba is taken
5nb
4o
15ceramic powder, BaNb
2o
6ceramic powder and product A also form mixed powder; The raw material taken is adopted wet ball-milling method mixing and ball milling 23 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, dries in an oven and obtain mixed powder;
E. in the mixed powder of steps d, binding agent is added and compressing after granulation, shaping raw stock is obtained at 600 DEG C of insulations, 2 hours binder removals, this life stock is placed in muffle furnace and is raised to 880 DEG C of insulations 4 hours with the speed of 6 DEG C/min from room temperature, after sintering, form microwave dielectric ceramic materials; The binding agent of the present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase of the ceramics sample after adopting x-ray diffractometer (XRD) analysis to sinter is Ba
5nb
4o
15phase and BaNb
2o
6phase two-phase.Adopt Agilent H98722ET vector grid analyzer test result: DIELECTRIC CONSTANT ε
r=43.1, quality factor q × f=9631.8GHz, there are very high quality factor; Temperature coefficient of resonance frequency τ
f=-7ppm/ DEG C, quality factor increase than embodiment 1; Compare compared with prior art, sintering temperature is reduced to 880 DEG C from 900 DEG C, avoids simultaneously and reacts with polyvinyl alcohol water solution, can have the ceramic diaphragm that preparation is finer and close; It also avoid and react with containing barium compound, LTCC technology needs can be met.
Embodiment five
Comprise: ywt% [(1-x) Ba
5nb
4o
15-xBaNb
2o
6]+zwt%A, wherein: A is CuO and HBO
3in mole than the ratio of 1:6.5 react at 1150 DEG C 3 little time after product; X=0.15, z=13, y=87.
The preparation method of the present embodiment low temperature sintering microwave dielectric ceramic materials, comprises the following steps:
A. Ba is prepared
5nb
4o
15ceramic powder:
By Ba
5nb
4o
15stoichiometric proportion take BaCO
3and Nb
2o
5raw material, adopts wet ball-milling method mixing and ball milling 24 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and within 4 hours, obtains Ba after drying in an oven 1150 DEG C of insulations
5nb
4o
15ceramic powder;
B. BaNb is prepared
2o
6ceramic powder:
By BaNb
2o
6stoichiometric proportion take BaCO
3and Nb
2o
5raw material, the raw material taken is adopted wet ball-milling method mixing and ball milling 23 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, 1150 DEG C of DEG C of insulations 2 hours after drying in an oven, cool to 940 DEG C of insulations with the speed of 4 DEG C/min and obtain BaNb in 5 hours
2o
6ceramic powder;
C.CuO and HBO
3reaction obtains product A:
By CuO and HBO
3mole than being the proportions of 1:6.5, add in ball grinder and adopt dry type ball-milling method mixing and ball milling 4 hours, obtain product A 1150 DEG C of insulations after 3 hours and pulverize;
D. Ba is taken
5nb
4o
15ceramic powder, BaNb
2o
6ceramic powder and product A also form mixed powder; The raw material taken is adopted wet ball-milling method mixing and ball milling 23 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, dries in an oven and obtain mixed powder;
E. in the mixed powder of steps d, binding agent is added and compressing after granulation, shaping raw stock is obtained at 550 DEG C of insulations, 3 hours binder removals, this life stock is placed in muffle furnace and is raised to 840 DEG C of insulations 3 hours with the speed of 3 DEG C/min from room temperature, after sintering, form microwave dielectric ceramic materials; The binding agent of the present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase of the ceramics sample after adopting x-ray diffractometer (XRD) analysis to sinter is Ba
5nb
4o
15phase and BaNb
2o
6phase two-phase.Adopt Agilent H98722ET vector grid analyzer test result: DIELECTRIC CONSTANT ε
r=42.6, quality factor q × f=10171.9GHz, there are very high quality factor; Temperature coefficient of resonance frequency τ
f=0ppm/ DEG C, quality factor and embodiment 1 are than high, and temperature coefficient of resonance frequency is zero; Compare compared with prior art, sintering temperature is reduced to 840 DEG C from 900 DEG C, avoids simultaneously and reacts with polyvinyl alcohol water solution, can have the ceramic diaphragm that preparation is finer and close; It also avoid and react with containing barium compound, LTCC technology needs can be met.
Embodiment six
Comprise: ywt% [(1-x) Ba
5nb
4o
15-xBaNb
2o
6]+zwt%A, wherein: A is CuO and HBO
3in mole than the ratio of 1:7.5 react at 1150 DEG C 4 little time after product; X=0.25, z=8, y=92.
The preparation method of the present embodiment low temperature sintering microwave dielectric ceramic materials, comprises the following steps:
A. Ba is prepared
5nb
4o
15ceramic powder:
By Ba
5nb
4o
15stoichiometric proportion take BaCO
3and Nb
2o
5raw material, adopts wet ball-milling method mixing and ball milling 24 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and within 4 hours, obtains Ba after drying in an oven 1150 DEG C of insulations
5nb
4o
15ceramic powder;
B. BaNb is prepared
2o
6ceramic powder:
By BaNb
2o
6stoichiometric proportion take BaCO
3and Nb
2o
5raw material, the raw material taken is adopted wet ball-milling method mixing and ball milling 23 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, 1150 DEG C of DEG C of insulations 2 hours after drying in an oven, cool to 940 DEG C of insulations with the speed of 4 DEG C/min and obtain BaNb in 5 hours
2o
6ceramic powder;
C.CuO and HBO
3reaction obtains product A:
By CuO and HBO
3mole than being the proportions of 1:7.5, add in ball grinder and adopt dry type ball-milling method mixing and ball milling 4 hours, obtain product A 1150 DEG C of insulations after 4 hours and pulverize;
D. Ba is taken
5nb
4o
15ceramic powder, BaNb
2o
6ceramic powder and product A also form mixed powder; The raw material taken is adopted wet ball-milling method mixing and ball milling 24 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, dries in an oven and obtain mixed powder;
E. in the mixed powder of steps d, binding agent is added and compressing after granulation, shaping raw stock is obtained at 600 DEG C of insulations, 2 hours binder removals, this life stock is placed in muffle furnace and is raised to 850 DEG C of insulations 2 hours with the speed of 4 DEG C/min from room temperature, after sintering, form microwave dielectric ceramic materials; The binding agent of the present embodiment is the polyvinyl alcohol water solution of concentration 3.5wt%.
The principal crystalline phase of the ceramics sample after adopting x-ray diffractometer (XRD) analysis to sinter is Ba
5nb
4o
15phase and BaNb
2o
6phase two-phase.Adopt Agilent H98722ET vector grid analyzer test result: DIELECTRIC CONSTANT ε
r=42.3, quality factor q × f=11171.9GHz, there are very high quality factor; Temperature coefficient of resonance frequency τ
f=-6ppm/ DEG C, quality factor and embodiment 1 are than high; Compare compared with prior art, sintering temperature is reduced to 850 DEG C from 900 DEG C, avoids simultaneously and reacts with polyvinyl alcohol water solution, can have the ceramic diaphragm that preparation is finer and close; It also avoid and react with containing barium compound, LTCC technology needs can be met.
According to the parameter comparison of above-described embodiment, microwave dielectric ceramic materials dielectric constant 42< ε of the present invention
r<44, quality factor q × f>8000GHz, temperature coefficient of resonance frequency-7ppm/ DEG C of < τ
f<5ppm/ DEG C; Reduce sintering temperature further, sintering temperature is lower than 880 DEG C simultaneously; Embodiment two, embodiment five and embodiment six are obviously better than other embodiment, and embodiment two is obviously better than embodiment five and embodiment six, is optimum proportioning and technological parameter.
In embodiment two, CuO and HBO
3the product of reaction is CuB
8o
13, and in other embodiment, this product is different from it, though can reach relative to the good effect of prior art, still has deficiency compared with embodiment two.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (5)
1. a preparation method for low-temperature sintered microwave dielectric ceramic material, is characterized in that: comprise the following steps:
A. Ba is prepared
5nb
4o
15ceramic powder; By Ba
5nb
4o
15stoichiometric proportion take BaCO
3and Nb
2o
5raw material, adopts wet ball-milling method mixing and ball milling 20 ~ 24 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and within 1 ~ 6 hour, obtains Ba after drying in an oven 1000 DEG C ~ 1200 DEG C insulations
5nb
4o
15ceramic powder;
B. BaNb is prepared
2o
6ceramic powder; By BaNb
2o
6stoichiometric proportion take BaCO
3and Nb
2o
5raw material, the raw material taken is adopted wet ball-milling method mixing and ball milling 20 ~ 24 hours with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder, 1000 DEG C ~ 1200 DEG C insulations 1 ~ 4 hour after drying in an oven, cool to 900 DEG C ~ 950 DEG C insulations with the speed of 2 ~ 5 DEG C/min and obtain BaNb in 1 ~ 6 hour
2o
6ceramic powder;
C. CuO and HBO
3reaction obtains product A; Described A is CuO and HBO
3in mole than 1:(5 ~ 9) ratio at 1000 DEG C ~ 1200 DEG C, react the product after 1 ~ 4 hour;
D. ywt% [(1-x) Ba is pressed
5nb
4o
15-xBaNb
2o
6] formula of+zwt%A, x=0.1 ~ 0.3,0<z<20, y+z=100 takes the Ba of step a gained
5nb
4o
15the BaNb of ceramic powder, step b gained
2o
6the product A powder of ceramic powder and step c gained, adopts wet ball-milling method mixing and ball milling 22 ~ 24 hour with absolute ethyl alcohol or deionized water for ball-milling medium adds in ball grinder by the raw material taken, and dries in an oven and obtains mixed powder;
E. in the mixed powder of steps d, add binding agent and compressing after granulation, the addition of bonding agent is the 1wt% ~ 3.5wt% of mixed powder quality in steps d, obtains shaping green billet after compressing at 500 DEG C ~ 600 DEG C insulations, 1 ~ 3 hour binder removal; Obtain microwave dielectric ceramic materials, heating rate 1.5 ~ 6 DEG C/min of sintering process after described green billet sintering, sintering temperature is 830 ~ 880 DEG C, and temperature retention time is 1 ~ 4 hour at this temperature.
2. the preparation method of low-temperature sintered microwave dielectric ceramic material according to claim 1, it is characterized in that: in step e, green billet is placed in Muffle furnace and sinters, and obtains microwave dielectric ceramic materials.
3. the preparation method of low-temperature sintered microwave dielectric ceramic material according to claim 1, is characterized in that: in step c, CuO and HBO
3add in ball grinder and adopt dry type ball-milling method mixing and ball milling obtain product A 1000 DEG C ~ 1200 DEG C insulations after 1 ~ 4 hour after 2 ~ 6 hours and pulverize.
4. the preparation method of low-temperature sintered microwave dielectric ceramic material according to claim 3, is characterized in that: CuO and HBO
3mole than for 1:(6 ~ 8).
5. the preparation method of low-temperature sintered microwave dielectric ceramic material according to claim 1, is characterized in that: in step e, and described binding agent is polyvinyl alcohol water solution, and concentration is 1.0wt% ~ 5.0wt%.
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| CN103553610B (en) * | 2013-10-30 | 2015-04-15 | 云南云天化股份有限公司 | Low-temperature sintered microwave dielectric ceramic material, preparation method and microwave device |
| CN104129993B (en) * | 2014-07-10 | 2015-10-07 | 上海大学 | A kind of reduction KNbO 3the method of base PTCR material sintering temperature |
| CN106699178A (en) * | 2015-11-18 | 2017-05-24 | 信昌电子陶瓷股份有限公司 | low-temperature co-fired ceramic microwave dielectric ceramic |
| CN113690561B (en) * | 2021-09-01 | 2022-07-29 | 深圳市动盈先进材料有限公司 | Preparation method of filter for 5G signal conversion |
| CN114105638B (en) * | 2021-12-31 | 2022-12-23 | 嘉兴佳利电子有限公司 | Medium dielectric constant low-temperature sintered microwave dielectric ceramic material and preparation method thereof |
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| CN101423392A (en) * | 2008-10-08 | 2009-05-06 | 东莞华科电子有限公司 | Low-temperature co-fired microwave dielectric ceramic material and preparation method thereof |
| CN101811869A (en) * | 2010-04-30 | 2010-08-25 | 华中科技大学 | Low-temperature sintering microwave medium ceramic material and preparation method thereof |
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