CN103145416A - Environment-friendly ultralow-temperature sintered microwave dielectric ceramic material and preparation method thereof - Google Patents
Environment-friendly ultralow-temperature sintered microwave dielectric ceramic material and preparation method thereof Download PDFInfo
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- CN103145416A CN103145416A CN2013100848571A CN201310084857A CN103145416A CN 103145416 A CN103145416 A CN 103145416A CN 2013100848571 A CN2013100848571 A CN 2013100848571A CN 201310084857 A CN201310084857 A CN 201310084857A CN 103145416 A CN103145416 A CN 103145416A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims description 42
- 238000000498 ball milling Methods 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 17
- 238000005469 granulation Methods 0.000 claims description 10
- 230000003179 granulation Effects 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 238000000748 compression moulding Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 10
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 238000003556 assay Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000009774 resonance method Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- MOVRNJGDXREIBM-UHFFFAOYSA-N aid-1 Chemical compound O=C1NC(=O)C(C)=CN1C1OC(COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)CO)C(O)C1 MOVRNJGDXREIBM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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Abstract
The invention discloses an environment-friendly ultralow-temperature sintered microwave dielectric ceramic material system and a preparation method thereof. The structure expression formula of the system is K2MoxO(3x+1)(x is equal to 2-4). The system can be sintered at very low temperature (460-550 DEG C), has excellent microwave dielectric performance (the dielectric constant ranges from 5 to 8, the quality factor Qf ranges from 30,000GHz to 50,000GHz, the frequency temperature coefficient ranges from minus 60ppm/DEG C to minus 93ppm/DEG C). The powder is prepared by adopting a solid phase synthesis method, and the presintering temperature ranges from 400 DEG C to 450 DEG C. The material system can be sintered jointly with Ag or Al, can be used for preparing low-temperature co-fired ceramic (LTCC) substrates, and is applied to a microwave resonator, a filter, a planar antenna and the like. The environment-friendly ultralow-temperature sintered microwave dielectric ceramic material system and the preparation method thereof meet the environment-friendly requirement, and are non-toxic and free from environment pollution.
Description
Technical field
The invention belongs to electronic ceramics and preparation field thereof, particularly be can be in 470-550 ° of C temperature range the environment-friendly type ultralow temperature-sintered microwave dielectric ceramic material system and preparation method thereof of densified sintering product.
Background technology
Along with the development of modern communications technology, more and more higher requirement has been proposed for the miniaturization of electronic product, portability, the aspect such as multi-functional, highly reliable and low-cost.LTCC is mainly used in the technical elements of high integration, high-performance electronic encapsulation, has huge potential aspect handiness, wiring density and the reliability of design.
Microwave-medium ceramics is as the key foundation material of LTCC technology, requirement has low sintering temperature (less than 900 ° of C), suitable specific inductivity, high quality factor, be bordering on zero temperature coefficient of resonance frequency and good thermostability, and the stupalith formula should be conducive to technical process, is easy to industrialization.Most traditional electronic ceramicss can not satisfy the LTCC technology to the requirement of material, and its reason is that the sintering temperature of pottery is too high.The exploitation low-temp sintered material has caused people's interest.
Microwave-medium ceramics realizes that low sintering main path has: appropriate sintering aid 1. adulterates---low melting point oxide or low melting glass; 2. adopt wet chemistry method to prepare the high powder of surfactivity; 3. adopt nano-powder; 4. adopt hot pressed sintering.In above these reduce the method for sintering temperature, consider that 4. 3. 2. the complexity of production cost, technique all be unfavorable for suitability for industrialized production.Method 1., cost is low, technique is simple, is low-temperature sintering method at present commonly used, but often additive can worsen the performance of pottery.Therefore, seeking the low microwave-medium ceramics system of novel intrinsic sintering temperature is one of direction of future development, particularly the material system of ultra-high dielectric coefficient (greater than 100) and ultralow dielectric (3-5).
The ultralow-temperature sintering microwave medium ceramic systems of existing open report mainly contains Te base Bi at present
2O
3– TeO
2, TiO
2– TeO
2, CaO – TeO
2, BaO-TiO
2-TeO
2With Mo base Bi
2O
3-MoO
3, Li
2O-Bi
2O
3-MoO
3, minimum sintering temperature reaches 520 ° of C, Te in these systems
2(Mo
0.95W
0.05) O
7520 ° of C sintering DIELECTRIC CONSTANT ε
r=13.9, Qf=25820GHz, τ
f=-12.8ppm/ ° C.Li
2Mo
4O
13At 520 ° of C sintering ε
r=8.8, Qf=7700GHz, τ
f=-66ppm/ ° C.Consider the costliness of the raw material of Te, and severe toxicity is arranged, be not suitable for a large amount of productions.In these sintered at ultra low temperature system stupaliths, component contains the lower oxide compound of a kind of fusing point at least.So the present invention has studied K
2O-MoO
3System found that this system material has good microwave dielectric property, ε
r=5～8, Qf=30000～50000GHz, τ
f=-60～-93ppm/ ° C, can burn altogether with Ag or Al electrode, chemical constitution and preparation technology are simple, particularly have ultralow sintering temperature (470-550 ° of C), are minimum in the present existing microwave-medium ceramics system of reporting.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned present technology, on the basis of not adding any sintering aid, provide ultralow temperature-sintered microwave dielectric ceramic material system and preparation method thereof, and satisfy the requirement of ltcc substrate material technology.
First purpose of the present invention is to provide three kinds of ultralow temperature-sintered microwave dielectric ceramic materials, after sintering, its microwave property is relative permittivity 5～8, microwave dielectric loss 30000～50000GHz, frequency-temperature coefficient-60～-93ppm/ ° C, topmost characteristics are to carry out sintering at low-down temperature (470～550 ° of C), and can burn altogether with Ag or Al electrode, chemical constitution and preparation technology are simple simultaneously.
For achieving the above object, the invention provides a kind of environment-friendly type ultralow temperature-sintered microwave dielectric ceramic material system, this stupalith structure expression is: K
2Mo
xO
3x+1, wherein, x=2～4, this system is carried out sintering and is made between 440 ° of C to 550 ° of C of ultralow sintering range.
Second purpose of the present invention is to provide the preparation method of above-mentioned ultralow temperature-sintered microwave dielectric ceramic material, and technique is simple.
For achieving the above object, the technical solution used in the present invention is:
A kind of preparation method of environment-friendly type ultralow temperature-sintered microwave dielectric ceramic material system is characterized in that: according to general formula K
2Mo
xO
3x+1, wherein, x=2～4 take raw material, after adopting a ball milling that raw material is mixed, carry out presintering at the temperature of 400-450 ° of C, then, carry out secondary ball milling, and at last by the compressing tablet sintering and get final product, wherein, the sintering temperature of compressing tablet sintering is 440-550 ° of C.
One time ball milling carries out in ball grinder, and adds in ball grinder zirconium ball and dehydrated alcohol are arranged, and wherein, according to mass ratio, zirconium ball: raw material: dehydrated alcohol is 2:1:1.
The parameter of a ball milling is: speed 150r/min, time 4h.
Put into again crucible after the powder drying that obtains after ball milling and carry out presintering.
The compressing tablet process of compressing tablet sintering is: adding weight percent in the powder after secondary ball milling is that 5% PVA carries out granulation, after granulation, gets 60-120 purpose powder, is pressed under the pressure of 300MPa.
After compression moulding, 390-440 ° of C insulation 4-5 hour, to get rid of PVA.
The present invention adopts the synthetic method of the most simple and effective solid state reaction to prepare stupalith system of the present invention.At first, carry out weighing according to formulating of recipe.Then, adopt a ball milling that raw material is mixed, the synthetic phase that needs of pre-burning at suitable temperature, and increase the activity of reacting, adopt secondary ball milling that synthetic powder is levigate.Obtain needed ceramics sample by the compressing tablet sintering at last.Through simple and effective like this preparation method, the specific inductivity of the ceramics sample that obtains changes between 5～8, quality factor q f is distributed in 30, between 000～50,000GHz, temperature coefficient of resonance frequency-60～-93ppm/ ° C between, sintering temperature is between 470～550 ° of C, can burn altogether with Ag or Al electrode, make it to be applicable to the needs of LTCC technology, enlarge its range of application.
Description of drawings
Fig. 1 is the XRD figure by the ceramic systems of the inventive method preparation.
Embodiment
Technical scheme of the present invention is achieved in that the structure representation general formula of ultralow-temperature sintering microwave medium pottery is K
2Mo
xO
3x+1, wherein, x=2～4.
Ultralow-temperature sintering microwave medium pottery step of preparation process of the present invention is as follows:
1) with chemical feedstocks K
2CO
3(purity is 99%) and MoO
3(purity is 99.5%) is by formula general formula K
2Mo
xO
3x+1Preparation, wherein x=2～4;
2) raw material that weighs up is put into ball grinder, according to the zirconium ball: the mass ratio of raw material: dehydrated alcohol=2:1:1 adds goal and dehydrated alcohol, is placed on planetary ball mill the rotating speed ball milling 4h with 150r/min after good seal;
3) powder after ball milling takes out oven dry (100 ° of C of bake out temperature), then puts into crucible respectively at 400-450 ° of C pre-burning 4h;
4) powder after pre-burning, manually levigate after, put into ball grinder, according to step 2) in same ratio, be placed on planetary ball mill the rotating speed ball milling 5h with 150r/min after good seal;
5) powder after ball milling is taken out oven dry (100 ° of C of bake out temperature), add the PVA of 5wt% to carry out granulation, get 60 orders to the powder between 120 orders, be pressed under the pressure of 300MPa, at 390-440 ° of C insulation 4-5h, PVA is got rid of.Then carry out sintering at 440-550 ° of C insulation 2h, obtain needed microwave dielectric ceramic materials.
Ultralow-temperature sintering microwave medium ceramic substrate material of the present invention has following characteristics: relatively low specific inductivity (5～8), lower dielectric loss (30,000～50,000GHz), temperature coefficient of resonance frequency low (TCF=-60～-93ppm/ ° C), ultralow sintering temperature (470～550 ° of C) can be burnt altogether with Ag or Al electrode, and chemical constitution and preparation technology are simple.The present invention meets environmental requirement, and is nontoxic, environmentally safe.
The present invention is according to the correlation theory of crystal chemistry and Dielectric Physics, and selecting low melting point oxide is initial starting material, with K
2O-MoO
3Low fever's compound in Binary Phase Diagram is the basis, adopts above process for solid phase synthesis, obtains the well behaved microwave dielectric ceramic materials of sintered microwave at ultralow temperature.
Embodiment 1:
Raw material K with purity assay
2CO
3And MoO
3Be mixed with main powder in the 1:2 ratio, then with the abundant mixing and ball milling of main powder 4 hours, after drying 400 ° of C pre-burnings 4 hours, then carried out again secondary ball milling 5 hours after the bulk sample after pre-burning being pulverized, add the 5wt%PVA granulation after levigate oven dry, sieve through 60 orders and 120 eye mesh screen bilayers, compression moulding on demand under the pressure of 300MPa (sheet or column), at 390 ° of C insulation 5h, PVA is got rid of, then sintering 2h becomes porcelain under 480 ° of C air, can obtain ultralow temperature-sintered microwave dielectric ceramic material.
The present invention uses network analyzer (8720ES Agilent) and incubator (DELTA9023, DeltaDesign) to adopt and closes microwave dielectric property and the temperature spectrum that the chamber resonance method has been tested sample.The calculation formula of TCF is as follows:
f
85And f
25Respectively TE when 85 ° of C and 25 ° of C
01 δResonant frequency under pattern.
The performance of this group stupalith reaches following index:
K
2Mo
2O
7Sinter porcelain in 480 ° of C air, the dielectric properties ε under microwave
r～6 (11.8GHz), quality factor q～3700, Qf～41, the temperature coefficient of resonance frequency TCF under 740GHz, microwave～-84ppm/ ° C (25-85 ° of C).
Embodiment 2:
Raw material K with purity assay
2CO
3And MoO
3Be mixed with main powder in the 1:3 ratio, then with the abundant mixing and ball milling of main powder 4 hours, after drying 450 ° of C pre-burnings 4 hours, then carried out again secondary ball milling 5 hours after the bulk sample after pre-burning being pulverized, add the 5wt%PVA granulation after levigate oven dry, sieve through 60 orders and 120 eye mesh screen bilayers, compression moulding on demand under the pressure of 300MPa (sheet or column), at 440 ° of C insulation 5h, PVA is got rid of, then sintering 2h becomes porcelain under 520 ° of C air, can obtain ultralow temperature-sintered microwave dielectric ceramic material.
The present invention uses network analyzer (8720ES Agilent) and incubator (DELTA9023, DeltaDesign) to adopt and closes microwave dielectric property and the temperature spectrum that the chamber resonance method has been tested sample.The calculation formula of TCF is as follows:
f
85And f
25Respectively TE when 85 ° of C and 25 ° of C
01 δResonant frequency under pattern.
The performance of this group stupalith reaches following index:
K
2Mo
3O
10Sinter porcelain in 520 ° of C air, the dielectric properties ε under microwave
r～5.6 (12.2GHz), quality factor q～3188, Qf～35, the temperature coefficient of resonance frequency TCF under 828GHz, microwave～-92ppm/ ° C (25-85 ° of C).
Embodiment 3:
Raw material K with purity assay
2CO
3And MoO
3Be mixed with main powder in the 1:4 ratio, then with the abundant mixing and ball milling of main powder 4 hours, after drying 450 ° of C pre-burnings 4 hours, then carried out again secondary ball milling 5 hours after the bulk sample after pre-burning being pulverized, add the 5wt%PVA granulation after levigate oven dry, sieve through 60 orders and 120 eye mesh screen bilayers, compression moulding on demand under the pressure of 300MPa (sheet or column), at 440 ° of C insulation 5h, PVA is got rid of, then sintering 2h becomes porcelain under 550 ° of C air, can obtain ultralow temperature-sintered microwave dielectric ceramic material.
The present invention uses network analyzer (8720ES Agilent) and incubator (DELTA9023, DeltaDesign) to adopt and closes microwave dielectric property and the temperature spectrum that the chamber resonance method has been tested sample.The calculation formula of TCF is as follows:
f
85And f
25Respectively TE when 85 ° of C and 25 ° of C
01 δResonant frequency under pattern.
The performance of this group stupalith reaches following index:
K
2Mo
4O
13Sinter porcelain in 550 ° of C air, the dielectric properties ε under microwave
r～5.3 (11.1GHz), quality factor q～4300, Qf～49, the temperature coefficient of resonance frequency TCF under 981GHz, microwave～-66ppm/ ° C (25-85 ° of C).
Embodiment 4:
Raw material K with purity assay
2CO
3And MoO
3Be mixed with main powder in the 1:1 ratio, then with the abundant mixing and ball milling of main powder 4 hours, after drying 500 ° of C pre-burnings 4 hours, then carried out again secondary ball milling 5 hours after the bulk sample after pre-burning being pulverized, add the 5wt%PVA granulation after levigate oven dry, sieve through 60 orders and 120 eye mesh screen bilayers, compression moulding on demand under the pressure of 300MPa (sheet or column), sticking 450 ° of C insulation 5h rows, then sintering 2h under 600 ° of C air, can obtain ultralow temperature-sintered microwave dielectric ceramic material.
The present invention uses network analyzer (8720ES Agilent) and incubator (DELTA9023, DeltaDesign) to adopt and closes microwave dielectric property and the temperature spectrum that the chamber resonance method has been tested sample.The calculation formula of TCF is as follows:
f
85And f
25Respectively TE when 85 ° of C and 25 ° of C
01 δResonant frequency under pattern.
The performance of this group stupalith reaches following index:
K
2MoO
4Sintering in 600 ° of C air, the dielectric properties ε under microwave
r～5.7 (11.05GHz), quality factor q～100, the temperature coefficient of resonance frequency TCF under Qf～1000GHz, microwave～-64ppm/ ° C (25-85 ° of C).
See also shown in Figure 1, by comparing embodiment 1,2,3,4, the K that visible the present invention proposes
2Mo
xO
3x+1(x=2～4) system has good microwave dielectric property (ε
r=5～8, Qf=30,000～50,000GHz, TCF=-60～-93ppm/ ° C).Advantage of the present invention is, this environmental protection new system not only can be at ultralow temperature sintering, and have good microwave dielectric property.
It is pointed out that according to technical scheme of the present invention, above-described embodiment can also be enumerated many, the results show a large amount of according to the applicant, the scope claims of the present invention propose all can reach purpose of the present invention.
Claims (8)
1. an environment-friendly type ultralow temperature-sintered microwave dielectric ceramic material system, is characterized in that, this stupalith structure expression is: K
2Mo
xO
3x+1, wherein, x=2～4, this system is carried out sintering and is made between 440 ° of C to 550 ° of C of ultralow sintering range.
2. the preparation method of an environment-friendly type ultralow temperature-sintered microwave dielectric ceramic material system, is characterized in that: according to general formula K
2Mo
xO
3x+1, wherein, x=2～4 take raw material, after adopting a ball milling that raw material is mixed, carry out presintering at the temperature of 400-450 ° of C, then, carry out secondary ball milling, and at last by the compressing tablet sintering and get final product, wherein, the sintering temperature of compressing tablet sintering is 440-550 ° of C.
3. method as claimed in claim 2, it is characterized in that: one time ball milling carries out in ball grinder, and adds zirconium ball and dehydrated alcohol in ball grinder, and wherein, according to mass ratio, zirconium ball: raw material: dehydrated alcohol is 2:1:1.
4. method as claimed in claim 3, it is characterized in that: the parameter of a ball milling is: speed 150r/min, time 4h.
5. method as claimed in claim 2 is characterized in that: put into crucible after the powder drying that obtains after ball milling again and carry out presintering.
6. method as claimed in claim 2, it is characterized in that: the compressing tablet process of compressing tablet sintering is: adding weight percent in the powder after secondary ball milling is that 5% PVA carries out granulation, after granulation, get 60-120 purpose powder, be pressed under the pressure of 300MPa.
7. method as claimed in claim 6, is characterized in that: after compression moulding, 390-440 ° of C insulation 4-5 hour, to get rid of PVA.
8. the preparation method of an environment-friendly type ultralow temperature-sintered microwave dielectric ceramic material system is characterized in that: comprise the following steps:
1) with raw material K
2CO
3And MoO
3By formula general formula K
2Mo
xO
3x+1Preparation, wherein x=2～4;
2) raw material that weighs up is put into ball grinder, according to the zirconium ball: the mass ratio of raw material: dehydrated alcohol=2:1:1 adds zirconium ball and dehydrated alcohol, is placed on planetary ball mill the rotating speed ball milling 4h with 150r/min after good seal;
3) powder after ball milling takes out oven dry, then puts into crucible at 400-450 ° of C pre-burning 4h;
4) powder after pre-burning, manually levigate after, put into ball grinder, according to step 2) identical method carries out secondary ball milling;
5) powder after secondary ball milling is taken out oven dry, add the PVA of weight percent 5% to carry out granulation, get 60 orders to the powder between 120 orders, be pressed, at 390-440 ° of C insulation 4-5h, PVA is got rid of, carry out sintering at 440-550 ° of C insulation 2h at last, obtain needed microwave dielectric ceramic materials.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110436894A (en) * | 2019-06-27 | 2019-11-12 | 深圳顺络电子股份有限公司 | A kind of low-k LTCC material and preparation method thereof |
| CN111187062A (en) * | 2020-01-13 | 2020-05-22 | 杭州电子科技大学 | CaSnSiO5-K2MoO4Base composite ceramic microwave material and preparation method thereof |
| CN113004026A (en) * | 2021-04-22 | 2021-06-22 | 无锡市高宇晟新材料科技有限公司 | LTCC microwave dielectric ceramic material and manufacturing method thereof |
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| CN110436894B (en) * | 2019-06-27 | 2022-10-21 | 深圳顺络电子股份有限公司 | Low-dielectric-constant LTCC material and preparation method thereof |
| CN111187062A (en) * | 2020-01-13 | 2020-05-22 | 杭州电子科技大学 | CaSnSiO5-K2MoO4Base composite ceramic microwave material and preparation method thereof |
| CN111187062B (en) * | 2020-01-13 | 2022-03-01 | 杭州电子科技大学 | CaSnSiO5-K2MoO4Base composite ceramic microwave material and preparation method thereof |
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