CN103936401B - A kind of preparation method of low dielectric constant microwave dielectric ceramic material - Google Patents
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 34
- 239000011521 glass Substances 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000428 dust Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 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
- 238000005245 sintering Methods 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 claims 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004891 communication Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000011162 core material Substances 0.000 abstract 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940024548 aluminum oxide Drugs 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
- 238000013461 design Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
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.The present invention uses common process and the equipment in LTCC field, prepares ceramic powder material by operations such as dispensing, ball milling, melted, broken, compounding, secondary ball milling, pelletizes.It is low that this ceramic material has dielectric constant, and dielectric loss is low, good temperature stability and processing characteristics, and raw material is cheap, and preparation technology is simple, and production cost is low, to equipment workshop condition without plurality of advantages such as particular/special requirements.The low dielectric microwave medium ceramic material that the present invention provides can use with the core material of microstrip line as electronic circuit substrate, resonator, wave filter, microwave base plate, electronic circuit, microwave communication, satellite communication and radar system also have important application prospect and economic benefit.
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 can be used for the diectric antenna, medium substrate and other related device that make in microwave communication system and microwave circuit, so being used widely on civilian and military.These are applied following requirement to low dielectric constant microwave dielectric ceramic material: the dielectric constant that (1) is stable；(2) low-dielectric loss (i.e. high quality factor Q*f (GHz) value)；(3) the temperature coefficient of resonance frequency τ f gone to zero, in order to ensure that device has good stability when temperature fluctuation.These requirements significantly limit ceramic material and are applied to practical devices.The existing low dielectric LTCC system microwave dielectric material of major part is made up of the alumina packing of borosilicate glass, ceramic packing and offer high intensity.But, borosilicate glass system usually contains and dielectric loss can be caused under lead, high frequency to increase, and this is by affecting the ceramic material proportion of goods damageds in high-frequency range, from environmental conservation angle, is also not suitable for the development of future electronic material.The present invention uses borate glass to be combined small amounts aluminum and silicon dioxide again, it is possible to allow the dielectric loss of ceramic material, high conductivity, strong mechanical performance realize harmony.
Now, international mature produces and is provided that mainly there are DuPont, Ferro and Heraeus tri-, the domestic tracking development that is still in the company of several porcelain with low dielectric constants, and most LTCC products depend on these porcelains of import.The such as MgO-Al of IBM Corporation's research and development2O3-SiO2Based material, its dielectric constant is 5.3～5.7, the CaO-B of Ferro company2O3-SiO2Based material, its dielectric constant is 7.0～9.0,901 series materials of DuPont, and its dielectric constant is 5.2～5.9.But, along with modularity and the surplus of electronic terminal product of future electronic element, the competition of Costco Wholesale is the fiercest, and the raw material design of domestic manufacturer's original adoption directly will be difficult to meet the requirement of price war from the way of external packing import.As can be seen here, the dependence to external LTCC porcelain, the LTCC porcelain of exploitation this country and the process for producing of advanced person are broken away from significant for the development of China's electronic material industry.
Summary of the invention
The present invention provides the preparation method of a kind of low dielectric constant microwave dielectric ceramic material, and the ceramic material that the present invention provides has low-k, low-loss and good temperature stability and processing characteristics.The technical problem to be solved is achieved through the following technical solutions.
A kind of preparation method of low dielectric constant microwave dielectric ceramic material, its technique is as follows:
1) dispensing, mixing, ball milling
By glass dust precursor material according to Ca (OH)237.1～38.4wt%, H3BO343.42～45.70wt%, Li2CO33.53～6.95wt%, La2O311.21～12.53wt% weigh mixing, add solvent and zirconia ball, employing wet ball grinding 8～10 hours；
2) dry, melt, crush
Through step 1) precursor material discharging after ball milling filters out zirconia ball, in 100～120 DEG C of drying, then at 1475 ± 25 DEG C of melt water quenchings, then the glass powder that crushing grinding becomes particle diameter to be 200～300 μm；
3) porcelain is compounding, ball milling, pelletize, tabletting, sintering
By step 2) glass dust for preparing and Al2O3According to glass dust 30～40wt%, Al2O35～10wt%, SiO253.19～60wt% weigh mixing, add solvent and zirconia ball, employing wet ball grinding 10～12 hours；Being subsequently adding the high polymer binder aqueous solution of 10～15wt%, ball milling 4～6 hours, mix homogeneously, pelletize, tabletting, binder removal sinters.
The dielectric constant of described low dielectric constant microwave dielectric ceramic material is 3.5～5.0@1MHz～4GHz, and dielectric loss is 0.0010～0.0050@1MHz～4GHz, and resonance temperature coefficient τ f=0～20ppm/ DEG C, insulation resistivity ρ are 2.1 × 1012Ω cm～4.0 × 1012Ω·cm。
Described step 1) described in solvent be deionized water or dehydrated alcohol.
Described step 1) described in glass dust precursor material, solvent, the weight proportion of zirconia ball be 1:1～2:1～4.
Described step 3) described in mixed powder, solvent, the weight proportion of zirconia ball be 1:1～2:1～4.
Described step 3) described in the high polymer binder aqueous solution that added be polyvinyl butyral resin (PVB) or the aqueous solution of polyvinyl alcohol (PVA), concentration is 10～15wt%.
Step 3) described in binder removal sintering process: by the potsherd pressed with the programming rate of 2 DEG C/min be warmed up to 450 DEG C be incubated 2 hours, it is warmed up to 650 DEG C again and is incubated 2 hours, it is warmed up to 850～900 DEG C of insulation 30min with the programming 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, the ceramic material of the present invention has the advantage that
1. dielectric constant is low, dielectric loss is low, meets high-frequency high-speed requirement；
The best 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/special requirement；
Product Green the most of the present invention, environmental protection, meet RoHS Directive, the harmful substances such as the most leaded, cadmium, hydrargyrum, Cr VI Cr6+, PBBs PBBs, PBDE PBDEs, reduce the environmental pollution brought in raw material, waste material and production process to the full extent.
Detailed description of the invention
The present invention is further illustrated by the following examples.
Embodiment 1
Weigh 37.1g Ca (OH)2；43.42g H3BO3；6.95g Li2CO3；11.21g La2O3Mixing, adds 200g deionized water and 400g zirconia ball, uses wet ball grinding 8 hours；
After glass raw material discharging after ball milling, in 100 DEG C of drying, then at 1475 DEG C of melt water quenchings, then the glass powder that crushing grinding becomes particle diameter to be 200 μm；
Weigh glass dust, 10g Al that 60g has prepared2O3、120g SiO2Mixing, adds 200g deionized water and 400g zirconia ball, uses wet ball grinding 10 hours；Add the PVA high polymer binder aqueous solution of 38ml 10wt%, ball milling 4 hours, mix homogeneously, pelletize compression molding；The potsherd pressed is warmed up to 450 DEG C with the programming rate of 2 DEG C/min in kiln formula sintering furnace and is incubated 2 hours, then be warmed up to 650 DEG C of insulations 2 hours；It is warmed up to 850 DEG C of insulation 30min with the programming rate of 3 DEG C/min, cools 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
Weigh 37.5g Ca (OH)2；44.5g H3BO3；5.5g Li2CO3；11.5g La2O3Mixing, adds 200g deionized water and 400g zirconia ball, uses wet ball grinding 9 hours；
After glass raw material discharging after ball milling, in 110 DEG C of drying, then at 1480 DEG C of melt water quenchings, then the glass powder that crushing grinding becomes particle diameter to be 250 μm；
Weigh glass dust, 14g Al that 64g has prepared2O3, 120g SiO2Mixing, adds 360g deionized water and 720g zirconia ball, uses wet ball grinding 10 hours；Add the PVA high polymer binder aqueous solution of 36ml 12wt%, ball milling 5 hours, mix homogeneously, pelletize compression molding；The potsherd pressed is warmed up to 450 DEG C with the programming rate of 2 DEG C/min in kiln formula sintering furnace and is incubated 2 hours, then be warmed up to 650 DEG C of insulations 2 hours；It is warmed up to 850 DEG C of insulation 30min with the programming rate of 3 DEG C/min, cools 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
Weigh 38g Ca (OH)2；45.2g H3BO3；4.6g Li2CO3；12g La2O3Mixing, adds 210g deionized water and 420g zirconia ball, uses wet ball grinding 9 hours；
After glass raw material discharging after ball milling, in 110 DEG C of drying, then at 1490 DEG C of melt water quenchings, then the glass powder that crushing grinding becomes particle diameter to be 250 μm；
Weigh glass dust, 18g Al that 70g has prepared2O3, 100g SiO2Mixing, adds 200g deionized water and 400g zirconia ball, uses wet ball grinding 11 hours；Add the PVA high polymer binder aqueous solution of 37.6ml 14wt%, ball milling 6 hours, mix homogeneously, pelletize compression molding；The potsherd pressed is warmed up to 450 DEG C with the programming rate of 2 DEG C/min in kiln formula sintering furnace and is incubated 2 hours, then be warmed up to 650 DEG C of insulations 2 hours；It is warmed up to 900 DEG C of insulation 30min with the programming rate of 3 DEG C/min, cools 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
Weigh 38.4g Ca (OH)2；45.7g H3BO3；3.54g Li2CO3；12.53g La2O3Mixing, adds 200g deionized water and 400g zirconia ball, uses wet ball grinding 10 hours；
After glass raw material discharging after ball milling, in 120 DEG C of drying, then at 1500 DEG C of melt water quenchings, then the glass powder that crushing grinding becomes particle diameter to be 300 μm；
Weigh glass dust, 20g Al that 80g has prepared2O3、90g SiO2Mixing, adds 190g deionized water and 360g zirconia ball, uses wet ball grinding 12 hours；Add the PVA high polymer binder aqueous solution of 42ml 15wt%, ball milling 6 hours, mix homogeneously, pelletize compression molding；The potsherd pressed is warmed up to 450 DEG C with the programming rate of 2 DEG C/min in kiln formula sintering furnace and is incubated 2 hours, then be warmed up to 650 DEG C of insulations 2 hours；It is warmed up to 900 DEG C of insulation 30min with the programming rate of 3 DEG C/min, cools 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 sinter under middle low temperature (Ts≤900 DEG C)；Dielectric constant 3.5～5.0@1MHz～4GHz of sample, dielectric loss is 0.0010～0.0050@1MHz～4GHz, and resonance temperature coefficient τ f=0～20ppm/ DEG C, insulation resistivity ρ are 2.1 × 1012Ω cm～4.0 × 1012Ω·cm。
Claims (7)
1. the preparation method of a low dielectric constant microwave dielectric ceramic material, it is characterised in that
Comprise the following steps:
1) dispensing, mixing, ball milling
By glass dust precursor material according to Ca (OH)237.1～38.4wt%,
H3BO343.42～45.70wt%, Li2CO33.53～6.95wt%, La2O311.21～12.53wt% claims
Amount mixing, adds solvent and zirconia ball, employing wet ball grinding 8～10 hours；
2) dry, melt, crush
Through step 1) precursor material discharging after ball milling filters out zirconia ball, in
100～120 DEG C of drying, then at 1475 ± 25 DEG C of melt water quenchings, then crushing grinding becomes the particle diameter to be
The glass powder of 200～300 μm；
3) porcelain is compounding, ball milling, pelletize, tabletting, sintering
By step 2) glass dust for preparing and Al2O3According to glass dust 30～40wt%,
Al2O35～10wt%, SiO253.19～60wt% weigh mixing, add solvent and zirconia ball, adopt
With wet ball grinding 10～12 hours；It is subsequently adding the high polymer binder aqueous solution of 10～15wt%,
Ball milling 4～6 hours, mix homogeneously, pelletize, tabletting, binder removal sinters.
2. the preparation side of low dielectric constant microwave dielectric ceramic material as claimed in claim 1
Method, it is characterised in that: the dielectric constant of described dielectric constant microwave ceramic material be 3.5～
5.0@1MHz～4GHz, dielectric loss is 0.0010～0.0050@1MHz～4GHz, resonance
Temperature coefficient τ f=0～20ppm/ DEG C, insulation resistivity ρ are 2.1 × 1012Ω cm～4.0 ×
1012Ω·cm。
3. the preparation side of low dielectric constant microwave dielectric ceramic material as claimed in claim 1
Method, it is characterised in that: step 1) described in solvent be deionized water or dehydrated alcohol.
4. the preparation side of low dielectric constant microwave dielectric ceramic material as claimed in claim 1
Method, it is characterised in that: step 1) described in glass dust precursor material, solvent, zirconium oxide
The weight proportion of ball is 1:1～2:1～4.
5. the preparation side of low dielectric constant microwave dielectric ceramic material as claimed in claim 1
Method, it is characterised in that: step 3) described in mixed powder, solvent, the weight of zirconia ball
Proportioning is 1:1～2:1～4.
6. the preparation side of low dielectric constant microwave dielectric ceramic material as claimed in claim 1
Method, it is characterised in that: step 3) described in the high polymer binder aqueous solution that added be poly-
Vinyl butyral (PVB) or the aqueous solution of polyvinyl alcohol (PVA), concentration is 10～15wt%.
7. the preparation side of low dielectric constant microwave dielectric ceramic material as claimed in claim 1
Method, it is characterised in that: step 3) described in binder removal sintering process be: the pottery that will press
Sheet is warmed up to 450 DEG C with the programming rate of 2 DEG C/min and is incubated 2 hours, then is warmed up to 650 DEG C of insulations
2 hours, it is warmed up to 850～900 DEG C of insulation 30min with the programming rate of 3 DEG C/min, with 3 DEG C
The cooling rate of/min cools to 400 DEG C, cools to room temperature with the furnace.
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| 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 |
| CN104370543B (en) * | 2014-11-10 | 2016-05-18 | 桂林理工大学 | Low-temperature sintering ultralow dielectric 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 |
| CN106673446B (en) * | 2017-01-05 | 2019-01-22 | 南京工程学院 | A kind of low dielectric high frequency glass-ceramic LTCC material 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 |
| CN109775993B (en) | 2019-03-01 | 2020-10-16 | 广东风华高新科技股份有限公司 | LTCC substrate and preparation method thereof |
| 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 |
| CN113461413B (en) * | 2021-07-02 | 2023-03-17 | 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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| JPS5328630A (en) * | 1976-08-30 | 1978-03-17 | Arukadeiebuitsuch Arekusandoru | Enamel for magnetic conductor made of steel used for electricity |
| JP5263112B2 (en) * | 2009-10-07 | 2013-08-14 | 旭硝子株式会社 | Ceramic raw material composition |
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|---|---|---|---|---|
| US5079194A (en) * | 1990-10-11 | 1992-01-07 | Aluminum Company Of America | Crystal growth inhibitor for glassy low dielectric inorganic composition |
| CN1121492A (en) * | 1995-06-12 | 1996-05-01 | 梁东明 | Nucleated glass and production technology |
| CN1974450A (en) * | 2005-11-16 | 2007-06-06 | E.I.内穆尔杜邦公司 | Lead free glass(es), thick film paste(s), tape composition(s) and low temperature cofired ceramic devices made therefrom |
| CN102173755A (en) * | 2011-01-20 | 2011-09-07 | 深圳振华富电子有限公司 | Low-temperature co-fired ceramic material, raw materials and preparation process thereof |
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