CN103936401A - Method for preparing low-dielectric-constant microwave dielectric ceramic material - Google Patents
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- CN103936401A CN103936401A CN201310596011.6A CN201310596011A CN103936401A CN 103936401 A CN103936401 A CN 103936401A CN 201310596011 A CN201310596011 A CN 201310596011A CN 103936401 A CN103936401 A CN 103936401A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000000498 ball milling Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000000919 ceramic Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 36
- 239000011521 glass Substances 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 229920005596 polymer binder Polymers 0.000 claims description 8
- 239000002491 polymer binding agent Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000013467 fragmentation Methods 0.000 claims description 2
- 238000006062 fragmentation reaction Methods 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004891 communication Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000011162 core material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 8
- 238000000748 compression moulding Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
The invention discloses a method for preparing a low-dielectric-constant microwave dielectric ceramic material by a solid phase synthesis method, and belongs to the raw ceramic powder preparation technology in the field of low temperature co-fired ceramic (LTCC). With adopting of a conventional process and conventional equipment of the low temperature co-fired ceramic field, the ceramic powder material is prepared through the procedures of proportioning, ball milling, melting, crushing, compounding, secondary ball milling, granulating and the like. The ceramic material has the many advantages of low dielectric constant, low dielectric loss, good temperature stability, good processability, cheap raw materials, simple preparation process, low production cost, no special requirements on the equipment workshop environment and the like. The low-dielectric-constant microwave dielectric ceramic material provided by the invention can be used as a core material of electronic circuit substrates, resonators, filters, microwave substrates and microstrip lines, and also has important application prospects and economic benefits in electronic circuits, microwave communication, satellite communication and radar systems.
Description
Technical field
The present invention uses solid-phase synthesis to prepare low dielectric constant microwave dielectric ceramic material, belongs to green powder technology of preparing in LTCC (LTCC) field.
Background technology
In recent years, low dielectric constant microwave dielectric ceramic material is owing to being used for making polyrod antenna, medium substrate and other related device of microwave communication system and microwave circuit, so be used widely on civilian and military.These application have following requirement to low dielectric constant microwave dielectric ceramic material: the DIELECTRIC CONSTANT ε that (1) is stable
r; (2) low-dielectric loss (being high quality factor Q*f (GHz) value); (3) temperature coefficient of resonance frequency going to zero
τ f , in order to ensure that device has good stability when the temperature fluctuation.These require greatly to have limited stupalith and are applied to practical devices.Most of existing low dielectric LTCC system microwave dielectric material is by borosilicate glass, ceramic packing and provide high-intensity alumina packing to form.But borosilicate glass system contains lead conventionally, under high frequency, can cause dielectric loss to increase, this from environment protection angle, is also not suitable for the development of following electronic material by affecting the wastage rate of stupalith in high-frequency range.The present invention uses borate glass compound a small amount of aluminum oxide and silicon-dioxide again, can allow dielectric loss, high conductivity, the strong mechanical performance of stupalith realize harmony.
Now, international mature is produced and can be provided the company of several porcelain with low dielectric constants to mainly contain tri-of DuPont, Ferro and Heraeus, and domestic still in following the tracks of development, most LTCC products depend on these porcelains of import.The for example MgO-Al of IBM Corporation's research and development
2o
3-SiO
2based material, its specific inductivity is the CaO-B of 5.3～5.7, Ferro company
2o
3-SiO
2based material, its specific inductivity is 901 series materials of 7.0～9.0, DuPont company, its specific inductivity is 5.2～5.9.But along with the modularization of following electronic component and the surplus of electronic terminal product, the competition of Costco Wholesale must be fiercer, the raw material design of domestic manufacturer's original adoption directly will be difficult to meet the requirement of rate war from the way of external packing import.As can be seen here, break away from the dependence to external LTCC porcelain, the process for producing of developing national LTCC porcelain and advanced person is significant for the development of China's electronic material industry.
Summary of the invention
The invention provides a kind of preparation method of low dielectric constant microwave dielectric ceramic material, stupalith provided by the invention has low-k, low-loss and good temperature stability and processing characteristics.Technical problem to be solved by this invention is achieved through the following technical solutions.
A preparation method for low dielectric constant microwave dielectric ceramic material, its technique is as follows:
1) batching, mixing, ball milling
By glass powder precursor material according to Ca (OH)
237.1 ~ 38.4wt%; H
3bO
343.42 ~ 45.70wt%; Li
2cO
33.34 ~ 6.95wt%; La
2o
311.21 ~ 12.53wt% weighs mixing, adds solvent and zirconia ball, adopts wet ball grinding 8 ~ 10 hours;
2) oven dry, melting, fragmentation
Precursor material discharging after step 1) ball milling filters out zirconia ball, in 100 ~ 120 DEG C of oven dry, then at 1475 ± 25 DEG C of melt water quenchings, then crushing grinding to become particle diameter be the glass powder of 200 ~ 300 μ m;
3) composite, the ball milling of porcelain, granulation, compressing tablet, sintering
By step 2) glass powder and the Al that prepare
2o
3according to glass powder 30 ~ 40wt%; Al
2o
35 ~ 10wt%; SiO
245 ~ 60wt% weighs mixing, adds solvent and zirconia ball, adopts wet ball grinding 10 ~ 12 hours; Then add the high polymer binder aqueous solution of 10 ~ 15wt%, ball milling 4 ~ 6 hours, mixes, granulation, compressing tablet, binder removal sintering.
The specific inductivity of described low dielectric constant microwave dielectric ceramic material is 3.5～5.0@1MHz～4GHz, dielectric loss is 0.0010～0.0050@1MHz～4GHz, resonance temperature factor τ f=0～20ppm/oC, insulation resistivity ρ is 2.1 × 1012 Ω cm～4.0 × 1012 Ω cm.
Solvent described in described step 1) is deionized water or dehydrated alcohol.
The weight proportion of glass powder precursor material, solvent, zirconia ball described in described step 1) is 1:1 ~ 2:1 ~ 4.
The weight proportion of mixed powder, solvent, zirconia ball described in described step 3) is 1:1 ~ 2:1 ~ 4.
The high polymer binder aqueous solution adding described in described step 3) is the aqueous solution of polyvinyl butyral acetal (PVB) or polyvinyl alcohol (PVA), and concentration is 10 ~ 15wt%.
Binder removal sintering process described in step 3): the ceramic plate pressing is warmed up to 450 DEG C of insulations 2 hours with the heat-up rate of 2 DEG C/min, be warmed up to again 650 DEG C of insulations 2 hours, be warmed up to 850～900 DEG C of insulation 30min with the heat-up rate of 3 DEG C/min, cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace.
Compared with prior art, stupalith of the present invention has following advantage:
1. specific inductivity is low, dielectric loss is low, meets high-frequency high-speed requirement;
2. good temperature stability;
3. suitability for secondary processing is superior;
4. raw material is cheap, and preparation technology is simple, and production cost is low, to equipment workshop without particular requirement;
5. Product Green of the present invention, environmental protection, meets the RoHS of European Union instruction, not leaded, cadmium, mercury, sexavalent chrome Cr
6+, the objectionable impurities such as Polybrominated biphenyl PBBs, Poly Brominated Diphenyl Ethers PBDEs, reduced to the full extent the environmental pollution bringing in raw material, waste material and production process.
Embodiment
The present invention further illustrates by the following examples.
embodiment 1
Take 37.1g Ca (OH)
2; 43.42g H
3bO
3; 6.95g Li
2cO
3; 11.21g La
2o
3mix, add 200g deionized water and 400g zirconia ball, adopt wet ball grinding 8 hours;
After glass raw material discharging after ball milling, in 100 DEG C of oven dry, then at 1475 DEG C of melt water quenchings, then crushing grinding to become particle diameter be the glass powder of 200 μ m;
Take glass powder, 10g Al that 60g has prepared
2o
3, 120g SiO
2mix, add 200g deionized water and 400g zirconia ball, adopt wet ball grinding 10 hours; Add the PVA high polymer binder aqueous solution of 38ml 10wt%, ball milling 4 hours, mixes, granulation compression molding; The ceramic plate pressing is warmed up to 450 DEG C of insulations 2 hours with the heat-up rate of 2 DEG C/min in kiln formula sintering oven, then is warmed up to 650 DEG C of insulations 2 hours; Be warmed up to 850 DEG C of insulation 30min with the heat-up rate of 3 DEG C/min, cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace, obtain low dielectric constant microwave dielectric ceramic material.
embodiment 2
Take 37.5g Ca (OH)
2; 44.5g H
3bO
3; 5.5g Li
2cO
3; 11.5g La
2o
3mix, add 200 g deionized waters and 400g zirconia ball, adopt wet ball grinding 9 hours;
After glass raw material discharging after ball milling, in 110 DEG C of oven dry, then at 1480 DEG C of melt water quenchings, then crushing grinding to become particle diameter be the glass powder of 250 μ m;
Take glass powder, 14g Al that 64g has prepared
2o
3, 120g SiO
2mix, add 360g deionized water and 720g zirconia ball, adopt wet ball grinding 10 hours; Add the PVA high polymer binder aqueous solution of 36ml 12wt%, ball milling 5 hours, mixes, granulation compression molding; The ceramic plate pressing is warmed up to 450 DEG C of insulations 2 hours with the heat-up rate of 2 DEG C/min in kiln formula sintering oven, then is warmed up to 650 DEG C of insulations 2 hours; Be warmed up to 850 DEG C of insulation 30min with the heat-up rate of 3 DEG C/min, cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace, obtain low dielectric constant microwave dielectric ceramic material.
embodiment 3
Take 38g Ca (OH)
2; 45.2g H
3bO
3; 4.6g Li
2cO
3; 12g La
2o
3mix, add 210g deionized water and 420g zirconia ball, adopt wet ball grinding 9 hours;
After glass raw material discharging after ball milling, in 110 DEG C of oven dry,, then at 1490 DEG C of melt water quenchings, then crushing grinding to become particle diameter be the glass powder of 250 μ m;
Take glass powder, 18g Al that 70g has prepared
2o
3, 100g SiO
2mix, add 200g deionized water and 400g zirconia ball, adopt wet ball grinding 11 hours; Add the PVA high polymer binder aqueous solution of 37.6ml 14wt%, ball milling 6 hours, mixes, granulation compression molding; The ceramic plate pressing is warmed up to 450 DEG C of insulations 2 hours with the heat-up rate of 2 DEG C/min in kiln formula sintering oven, then is warmed up to 650 DEG C of insulations 2 hours; Be warmed up to 900 DEG C of insulation 30min with the heat-up rate of 3 DEG C/min, cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace, obtain low dielectric constant microwave dielectric ceramic material.
embodiment 4
Take 38.4g Ca (OH)
2; 45.7g H
3bO
3; 3.54g Li
2cO
3; 12.53g La
2o
3mix, add 200g deionized water and 400g zirconia ball, adopt wet ball grinding 10 hours;
After glass raw material discharging after ball milling, in 120 DEG C of oven dry, then at 1500 DEG C of melt water quenchings, then crushing grinding to become particle diameter be the glass powder of 300 μ m;
Take glass powder, 20g Al that 80g has prepared
2o
3, 90g SiO
2mix, add 190g deionized water and 360g zirconia ball, adopt wet ball grinding 12 hours; Add the PVA high polymer binder aqueous solution of 42ml 15wt%, ball milling 6 hours, mixes, granulation compression molding; The ceramic plate pressing is warmed up to 450 DEG C of insulations 2 hours with the heat-up rate of 2 DEG C/min in kiln formula sintering oven, then is warmed up to 650 DEG C of insulations 2 hours; Be warmed up to 900 DEG C of insulation 30min with the heat-up rate of 3 DEG C/min, cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace, obtain low dielectric constant microwave dielectric ceramic material.
Table 1 embodiment of the present invention test result
As known from Table 1, all samples all can be at the lower sintering of middle low temperature (Ts≤900 DEG C); Specific inductivity 3.5～5.0@1MHz～4GHz of sample, dielectric loss is 0.0010～0.0050@1MHz～4GHz, resonance temperature factor τ
f=0～20ppm/ DEG C, insulation resistivity ρ is 2.1 × 10
12Ω cm～4.0 × 10
12Ω cm.
Claims (7)
1. a preparation method for low dielectric constant microwave dielectric ceramic material, is characterized in that comprising the following steps:
1) batching, mixing, ball milling
By glass powder precursor material according to Ca (OH)
237.1 ~ 38.4wt%; H
3bO
343.42 ~ 45.70wt%; Li
2cO
33.34 ~ 6.95wt%; La
2o
311.21 ~ 12.53wt% weighs mixing, adds solvent and zirconia ball, adopts wet ball grinding 8 ~ 10 hours;
2) oven dry, melting, fragmentation
Precursor material discharging after step 1) ball milling filters out zirconia ball, in 100 ~ 120 DEG C of oven dry, then at 1475 ± 25 DEG C of melt water quenchings, then crushing grinding to become particle diameter be the glass powder of 200 ~ 300 μ m;
3) composite, the ball milling of porcelain, granulation, compressing tablet, sintering
By step 2) glass powder and the Al that prepare
2o
3according to glass powder 30 ~ 40wt%; Al
2o
35 ~ 10wt%; SiO
245 ~ 60wt% weighs mixing, adds solvent and zirconia ball, adopts wet ball grinding 10 ~ 12 hours; Then add the high polymer binder aqueous solution of 10 ~ 15wt%, ball milling 4 ~ 6 hours, mixes, granulation, compressing tablet, binder removal sintering.
2. the preparation method of low dielectric constant microwave dielectric ceramic material as claimed in claim 1, it is characterized in that: the specific inductivity of described dielectric constant microwave stupalith is 3.5～5.0@1MHz～4GHz, dielectric loss is 0.0010～0.0050@1MHz～4GHz, resonance temperature factor τ f=0～20ppm/oC, insulation resistivity ρ is 2.1 × 1012 Ω cm～4.0 × 1012 Ω cm.
3. the preparation method of low dielectric constant microwave dielectric ceramic material as claimed in claim 1, is characterized in that: solvent described in step 1) is deionized water or dehydrated alcohol.
4. the preparation method of low dielectric constant microwave dielectric ceramic material as claimed in claim 1, is characterized in that: the weight proportion of the precursor material of glass powder described in step 1), solvent, zirconia ball is 1:1 ~ 2:1 ~ 4.
5. the preparation method of low dielectric constant microwave dielectric ceramic material as claimed in claim 1, is characterized in that: the weight proportion of mixed powder described in step 3), solvent, zirconia ball is 1:1 ~ 2:1 ~ 4.
6. the preparation method of low dielectric constant microwave dielectric ceramic material as claimed in claim 1, it is characterized in that: the high polymer binder aqueous solution adding described in step 3) is the aqueous solution of polyvinyl butyral acetal (PVB) or polyvinyl alcohol (PVA), and concentration is 10 ~ 15wt%.
7. the preparation method of low dielectric constant microwave dielectric ceramic material as claimed in claim 1, it is characterized in that: the binder removal sintering process described in step 3) is: the ceramic plate pressing is warmed up to 450 DEG C of insulations 2 hours with the heat-up rate of 2 DEG C/min, be warmed up to again 650 DEG C of insulations 2 hours, be warmed up to 850～900 DEG C of insulation 30min with the heat-up rate of 3 DEG C/min, cool to 400 DEG C with the cooling rate of 3 DEG C/min, cool to room temperature with the furnace.
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| CN201310596011.6A CN103936401B (en) | 2013-11-25 | 2013-11-25 | A kind of preparation method of low dielectric constant microwave dielectric ceramic material |
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| CN103936401B CN103936401B (en) | 2016-08-17 |
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ID=51184324
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370543A (en) * | 2014-11-10 | 2015-02-25 | 桂林理工大学 | Low-temperature sintering ultra-low dielectric constant microwave dielectric ceramic Ca3LaSmB4O12 |
| CN104319469B (en) * | 2014-10-16 | 2017-02-15 | 云南云天化股份有限公司 | Preparation method for micro-strip ceramic antenna |
| CN106673446A (en) * | 2017-01-05 | 2017-05-17 | 南京工程学院 | Low-dielectric-constant high-frequency glass ceramic LTCC material and preparation method thereof |
| CN106747357A (en) * | 2016-12-22 | 2017-05-31 | 广东风华高新科技股份有限公司 | LTCC and preparation method thereof |
| CN107140963A (en) * | 2017-04-20 | 2017-09-08 | 常州创索新材料科技有限公司 | A kind of preparation method of compound electromagnetic wave transparent material |
| WO2020177368A1 (en) * | 2019-03-01 | 2020-09-10 | 广东风华高新科技股份有限公司 | Ltcc substrate and preparation method therefor |
| CN113174098A (en) * | 2021-04-22 | 2021-07-27 | 桂林电子科技大学 | Anti-hydrolysis boric acid-based microwave dielectric polymer ceramic material and preparation method thereof |
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| CN104370543A (en) * | 2014-11-10 | 2015-02-25 | 桂林理工大学 | Low-temperature sintering ultra-low dielectric constant microwave dielectric ceramic Ca3LaSmB4O12 |
| CN106747357B (en) * | 2016-12-22 | 2019-12-06 | 广东风华高新科技股份有限公司 | Low-temperature co-fired ceramic and preparation method thereof |
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| JP2021517101A (en) * | 2019-03-01 | 2021-07-15 | 広東風華高新科技股▲フン▼有限公司Guangdong Fenghua Advanced Technology Holding Co., Ltd. | LTCC substrate and its manufacturing method |
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| CN113174098B (en) * | 2021-04-22 | 2022-08-19 | 桂林电子科技大学 | Anti-hydrolysis boric acid-based microwave dielectric polymer ceramic material and preparation method thereof |
| CN113461413A (en) * | 2021-07-02 | 2021-10-01 | 广东风华高新科技股份有限公司 | LTCC ceramic material and preparation method and application thereof |
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