CN113292338B - A kind of Ba-Co-V-based low-dielectric and low-fire microwave ceramic material and preparation method thereof - Google Patents
A kind of Ba-Co-V-based low-dielectric and low-fire microwave ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 18
- 229910020516 Co—V Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 29
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 29
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 19
- 238000005266 casting Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000012776 electronic material Substances 0.000 abstract description 2
- 239000003989 dielectric material Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 description 20
- 238000001816 cooling Methods 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- 238000009472 formulation Methods 0.000 description 9
- 238000000280 densification Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000009766 low-temperature sintering Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910002971 CaTiO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
本发明属于电子材料技术领域，具体涉及一种Ba‑Co‑V基低介低烧微波陶瓷材料及其制备方法，其烧结温度低，且具有高Q*f值和正τf值，可应用于LTCC技术领域。本发明在具有高微波介电性能的Ba3(VO4)2陶瓷基础上，未添加降烧剂通过调整原料配比，首次采用Co2+取代Ba3(VO4)2中的Ba2+，通过不同的取代量，在900℃～950℃低温致密烧结，获得了τf为+14.5ppm/℃～+23.8ppm/℃,Q*f为25318GHz～54,063GHz的Ba‑Co‑V基低介微波介电陶瓷材料；由于未添加助烧剂B2O3，因此避免了后期LTCC领域应用对流延工艺的影响，可作为微波介质陶瓷τf调节材料有效应用于LTCC技术领域。
The invention belongs to the technical field of electronic materials, and in particular relates to a Ba-Co-V-based low-dielectric and low-fire microwave ceramic material and a preparation method thereof, which have low sintering temperature, high Q*f value and positive τf value, and can be applied to LTCC technology field. Based on Ba 3 (VO 4 ) 2 ceramics with high microwave dielectric properties, the present invention uses Co 2+ to replace Ba 2+ in Ba 3 (VO 4 ) 2 for the first time by adjusting the ratio of raw materials without adding a sintering agent. , through different substitution amounts, sintered at low temperature of 900℃～950℃, Ba‑Co‑V-based low-dielectric low-dielectric materials with τf of +14.5ppm/℃～+23.8ppm/℃ and Q*f of 25318GHz～54,063GHz were obtained Microwave dielectric ceramic material; because no sintering aid B 2 O 3 is added, the influence of later LTCC application on the casting process is avoided, and it can be effectively used as a microwave dielectric ceramic τf adjustment material in the LTCC technical field.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to a Ba-Co-V-based low-dielectric low-sintering microwave ceramic material and a preparation method thereof.
Background
The rapid development of electronic communication, in particular to the increasing importance of microwave frequency band communication (300 MHz-300 GHz), is widely applied to the fields of mobile handheld phones, Bluetooth, radars, broadcast televisions and the like. Therefore, the development of microwave devices, such as resonators, filters, dielectric antennas, etc., has been increasingly demanded. The microwave dielectric ceramic has controllable size, and an integrated circuit formed by a resonator, a microstrip line and the like manufactured by using the microwave dielectric ceramic can enable the size of a device to reach millimeter level, so that the microwave dielectric ceramic becomes a basic and key material.
The low temperature co-fired ceramic technology (LTCC for short) is taken as a multidisciplinary crossed integrated assembly technology, is mainly applied to the field of advanced passive integration and hybrid circuit packaging at present, particularly the technical field of high frequency, high speed and high reliability, is more prominent, and can be widely applied to the fields of manufacturing passive integrated devices such as filters, electric bridges, baluns, power dividers, antennas and the like in batches, ceramic substrates and the like. One of the key materials, microwave dielectric ceramics, has received attention from researchers due to its high quality factor, excellent high frequency characteristics, good processing characteristics and stability. To lower the sintering temperature, B is generally used2O3,Bi2O3The addition of the oxide or the fluxing agent with low melting point is realized by a liquid phase mass transfer mechanism; by adding TiO2,CaTiO3And the material with the positive temperature resonance frequency coefficient adjusts the temperature resonance frequency coefficient to be close to zero. However, the added resonant frequency temperature coefficient adjusting material generally has the defects of high dielectric constant, low Q f, high sintering temperature and the like, so that the microwave dielectric property of the ceramic is greatly deteriorated and the sintering temperature is influenced, thereby greatly limiting the application range of the material.
Ba3(VO4)2The dielectric ceramic has the characteristics of low dielectric constant, high Q & ltf & gt, larger positive tau & ltf & gt and the like, is a good resonant frequency temperature coefficient regulating material, is usually used as a tau & ltf & gt regulator to regulate tau & ltf & gt of microwave dielectric ceramic to be nearly zero, so that the integrity of signals during transmission is ensured, but the densification temperature of the dielectric ceramic is usually more than 1100 ℃, so that the application in the field of LTCC is limited. To achieve low temperature sintering, researchers are directed to Ba3(VO4)2Has been subjected to a great deal of modification studies. Ryosuke Umemura et al by adding a sintering aid B2O3Will Ba3(VO4)2The sintering temperature is reduced to 925 ℃, tauf is 27.4-66.1 ppm/DEG C, but the Q f value is reduced to 41,065GHz, and a sintering aid B is introduced2O3Resulting in the unusable post-casting process and silver infiltration phenomenon (due to a large amount of B)2O3Caused by the interaction of the sintering aid and the glass in the Ag paste), so that the sintering aid cannot be really applied to the manufacture of LTCC devices.
Disclosure of Invention
Aiming at the problems or the defects, the existing Ba is solved3(VO4)2As a positive temperature coefficient adjusting material, the invention provides a Ba-Co-V based low-dielectric low-firing microwave ceramic material and a preparation method thereof, which solve the problem that the low-temperature sintering is difficult to realize and the application of the material in the field of LTCC under the condition of meeting high Q & ltf & gt and positive tau & ltf & gt values, and realize the Ba-Co-V based low-dielectric low-firing microwave ceramic material3(VO4)2The material has the advantages of low-temperature densification and good sintering property, keeps good microwave dielectric property, and can be applied to the field of LTCC.
In order to realize the technical purpose, the specific technical scheme is as follows:
a low-dielectric low-sintering Ba-Co-V microwave ceramic material with high Q f value and positive tau f value and its general chemical formula is B3- xCox(VO4)2Wherein x is 0.05-0.5; tau f is +14.5 ppm/DEG C to +23.8 ppm/DEG C, and Q f is 25318GHz to 54,063 GHz.
By using BaCO3CoO and V2O5Is taken as raw material and is mixed according to molar ratio BaCO3：CoO：V2O52.5-2.95: 0.05-0.5: 1, prepared by a solid phase process, wherein BaCO3The molar ratio to CoO is reduced; the presintering temperature in the solid phase method is 700-800 ℃, and the sintering temperature is 900-950 ℃.
The preparation method of the Ba-Co-V based low-dielectric microwave ceramic material comprises the following steps:
And 3, pre-sintering the ball-milling powder obtained in the step 2 at 700-800 ℃, keeping the temperature for 2-3 h, and increasing the temperature at the rate of 1-2 ℃/min.
Step 4, mixing the product obtained in the step 3 according to the following materials: deionized water: the mass ratio of the ball is 1: 1: 1.2-1.5, the rotation speed of the ball mill is 250 r/min-300 r/min, and the ball milling time is 8 h-12 h; and then drying at 80-120 ℃, adding 8-12 wt% (the PVA aqueous solution accounts for the percentage of the total mass) of PVA aqueous solution (the concentration is 10 wt%) as a binder for granulation, and performing compression molding at 8-10 MPa for 30-60 s.
Step 5, sintering the sample obtained in the step 4 at 900-950 ℃, wherein the heating rate is 1-2 ℃/min, the heat preservation time is 4-6 h, and the Ba-Co-V based low dielectric microwave dielectric ceramic material B with positive tau f value can be obtained after the sample is naturally cooled3-xCox(VO4)2。
The invention has high microwave dielectric property of Ba3(VO4)2On the basis of ceramics, Co is adopted for the first time by adjusting the raw material proportion without adding a sintering reducing agent2+Substituted Ba3(VO4)2Of Ba2+Through different substitution amounts, the Ba-Co-V based low dielectric microwave dielectric ceramic material with tau f of +14.5 ppm/DEG C to +23.8 ppm/DEG C and Q x f of 25318GHz to 54,063GHz is obtained by low-temperature compact sintering at 900 ℃ -950 ℃; because the sintering aid B is not added2O3Therefore, the influence of later-stage LTCC field application on the tape casting process is avoided, and the microwave dielectric ceramic τ f adjusting material can be effectively applied to the LTCC technical field.
Drawings
FIG. 1 is a process flow diagram of the solid phase reaction method for preparing materials according to the present invention;
FIG. 2 shows Ba in examples 1 to 103-xCox(VO4)2XRD pattern of (1), wherein x denotes Co2+The molar ratio of (A) to (B);
FIG. 3 shows Ba in examples 1 to 103-xCox(VO4)2Relative density value of (2), wherein x denotes Co2+The molar ratio of (A) to (B);
FIG. 4 shows Ba in examples 1,2,5,6,7 and 93-xCox(VO4)2SEM picture of (1), wherein x denotes Co2+The molar ratio of (A) to (B);
FIG. 5 shows Ba in examples 1 to 103-xCox(VO4)2τ f value of (1), where x denotes Co2+The molar ratio of (A) to (B);
FIG. 6 shows Ba in examples 1 to 103-xCox(VO4)2Wherein x denotes Co2+The molar ratio of (A) to (B);
FIG. 7 shows Ba in example 62.7Co0.3(VO4)2SEM picture after co-firing with Ag paste.
FIG. 8 shows Ba in example 62.7Co0.3(VO4)2The material is used for preparing a raw ceramic tile real object picture.
FIG. 9 shows Ba in example 62.7Co0.3(VO4)2The green ceramic chip made of the material adopts Ag slurry to print the obtained circuit pattern.
Detailed Description
The following examples are prepared by the aforementioned solid phase method of the present invention and are described in detail below to further illustrate the technical effects of the present invention.
Example 1:
(1) the material Ba is prepared by adopting the following raw material components and the content thereof2.95Co0.05(VO4)2：
Table 1: EXAMPLE 1 formulation Table (unit: mol)
| BaCO3 | V2O5 | CoO |
| 2.95 | 1 | 0.05 |
(2) The raw materials are weighed according to the formula proportion in the table 1, and are subjected to ball milling mixing, drying, crushing and sieving, pre-sintering, granulation, molding and sintering in sequence to obtain the material with excellent microwave dielectric property and positive tau f. Wherein the pre-sintering temperature is 800 ℃, the molding pressure is 10MPa, the pressure maintaining time is 30s, the sintering temperature is 950 ℃, the heating rate and the cooling rate are 2 ℃/min, the heat preservation time is 64h, and the temperature is naturally cooled after being reduced to 700 ℃.
Example 2:
(1) the material Ba is prepared by adopting the following raw material components and the content thereof2.9Co0.1(VO4)2：
Table 2: EXAMPLE 2 formulation Table (unit: mol)
| BaCO3 | V2O5 | CoO |
| 2.9 | 1 | 0.1 |
(2) The raw materials are weighed according to the formula proportion in the table 2, and are sequentially subjected to ball milling mixing, drying, crushing and sieving, presintering, granulation, molding and sintering to obtain the material with excellent microwave dielectric property and positive tau f. Wherein the pre-sintering temperature is 800 ℃, the molding pressure is 10MPa, the pressure maintaining time is 30s, the sintering temperature is 950 ℃, the heating rate and the cooling rate are 2 ℃/min, the heat preservation time is 64h, and the temperature is naturally cooled after being reduced to 700 ℃.
Example 3:
(1) the material Ba is prepared by adopting the following raw material components and the content thereof2.85Co0.15(VO4)2：
Table 3: EXAMPLE 3 recipe Table (unit: mol)
| BaCO3 | V2O5 | CoO |
| 2.85 | 1 | 0.15 |
(2) The raw materials are weighed according to the formula proportion in the table 3, and are subjected to ball milling mixing, drying, crushing and sieving, pre-sintering, granulation, molding and sintering in sequence to obtain the material with excellent microwave dielectric property and positive tau f. Wherein the pre-sintering temperature is 800 ℃, the molding pressure is 10MPa, the pressure maintaining time is 30s, the sintering temperature is 950 ℃, the heating rate and the cooling rate are 2 ℃/min, the heat preservation time is 64h, and the temperature is naturally cooled after being reduced to 700 ℃.
Example 4:
(1) the material Ba is prepared by adopting the following raw material components and the content thereof2.8Co0.2(VO4)2：
Table 4: EXAMPLE 4 formulation Table (unit: mol)
| BaCO3 | V2O5 | CoO |
| 2.8 | 1 | 0.2 |
(2) The raw materials are weighed according to the formula proportion in the table 4, and are subjected to ball milling mixing, drying, crushing and sieving, pre-sintering, granulation, molding and sintering in sequence to obtain the material with excellent microwave dielectric property and positive tau f. Wherein the pre-sintering temperature is 800 ℃, the molding pressure is 10MPa, the pressure maintaining time is 30s, the sintering temperature is 925 ℃, the heating rate and the cooling rate are 2 ℃/min, the heat preservation time is 64h, and the temperature is naturally cooled after being reduced to 700 ℃.
Example 5:
(1) the material Ba is prepared by adopting the following raw material components and the content thereof2.75Co0.25(VO4)2：
Table 5: EXAMPLE 5 formulation Table (unit: mol)
| BaCO3 | V2O5 | CoO |
| 2.75 | 1 | 0.25 |
(2) The raw materials are weighed according to the formula proportion in the table 5, and are subjected to ball milling mixing, drying, crushing and sieving, pre-sintering, granulation, molding and sintering in sequence to obtain the material with excellent microwave dielectric property and positive tau f. Wherein the pre-sintering temperature is 800 ℃, the molding pressure is 10MPa, the pressure maintaining time is 30s, the sintering temperature is 925 ℃, the heating rate and the cooling rate are 2 ℃/min, the heat preservation time is 64h, and the temperature is naturally cooled after being reduced to 700 ℃.
Example 6:
(1) the material Ba is prepared by adopting the following raw material components and the content thereof2.7Co0.3(VO4)2：
Table 6: EXAMPLE 6 formulation Table (unit: mol)
| BaCO3 | V2O5 | CoO |
| 2.7 | 1 | 0.3 |
(2) The raw materials are weighed according to the formula proportion in the table 6, and are subjected to ball milling mixing, drying, crushing and sieving, pre-sintering, granulation, molding and sintering in sequence to obtain the material with excellent microwave dielectric property and positive tau f. Wherein the pre-sintering temperature is 800 ℃, the molding pressure is 10MPa, the pressure maintaining time is 30s, the sintering temperature is 925 ℃, the heating rate and the cooling rate are 2 ℃/min, the heat preservation time is 64h, and the temperature is naturally cooled after being reduced to 700 ℃.
Example 7:
(1) the material Ba is prepared by adopting the following raw material components and the content thereof2.65Co0.35(VO4)2：
Table 7: EXAMPLE 7 formulation Table (Unit: mol)
| BaCO3 | V2O5 | CoO |
| 2.65 | 1 | 0.35 |
(2) The raw materials are weighed according to the formula proportion in the table 7, and are subjected to ball milling mixing, drying, crushing and sieving, pre-sintering, granulation, molding and sintering in sequence to obtain the material with excellent microwave dielectric property and positive tau f. Wherein the pre-sintering temperature is 800 ℃, the molding pressure is 10MPa, the pressure maintaining time is 30s, the sintering temperature is 925 ℃, the heating rate and the cooling rate are 2 ℃/min, the heat preservation time is 64h, and the temperature is naturally cooled after being reduced to 700 ℃.
Example 8:
(1) the material Ba is prepared by adopting the following raw material components and the content thereof2.6Co0.4(VO4)2：
Table 8: EXAMPLE 8 formulation Table (unit: mol)
| BaCO3 | V2O5 | CoO |
| 2.6 | 1 | 0.4 |
(2) The raw materials are weighed according to the formula proportion in the table 8, and are subjected to ball milling mixing, drying, crushing and sieving, pre-sintering, granulation, molding and sintering in sequence to obtain the material with excellent microwave dielectric property and positive tau f. Wherein the pre-sintering temperature is 800 ℃, the molding pressure is 10MPa, the pressure maintaining time is 30s, the sintering temperature is 900 ℃, the heating rate and the cooling rate are 2 ℃/min, the heat preservation time is 64h, and the temperature is naturally cooled after being reduced to 700 ℃.
Example 9:
(1) the material Ba is prepared by adopting the following raw material components and the content thereof2.55Co0.45(VO4)2：
Table 9: example 9 formulation Table (unit: mol)
| BaCO3 | V2O5 | CoO |
| 2.55 | 1 | 0.45 |
(2) The raw materials are weighed according to the formula proportion in the table 9, and are subjected to ball milling mixing, drying, crushing and sieving, pre-sintering, granulation, molding and sintering in sequence to obtain the material with excellent microwave dielectric property and positive tau f. Wherein the pre-sintering temperature is 800 ℃, the molding pressure is 10MPa, the pressure maintaining time is 30s, the sintering temperature is 900 ℃, the heating rate and the cooling rate are 2 ℃/min, the heat preservation time is 64h, and the temperature is naturally cooled after being reduced to 700 ℃.
Example 10:
(1) the material Ba is prepared by adopting the following raw material components and the content thereof2.5Co0.5(VO4)2：
Table 10: EXAMPLE 10 formulation Table (unit: mol)
| BaCO3 | V2O5 | CoO |
| 2.5 | 1 | 0.5 |
(2) The raw materials are weighed according to the formula proportion in the table 3, and are subjected to ball milling mixing, drying, crushing and sieving, pre-sintering, granulation, molding and sintering in sequence to obtain the material with excellent microwave dielectric property and positive tau f. Wherein the pre-sintering temperature is 800 ℃, the molding pressure is 10MPa, the pressure maintaining time is 30s, the sintering temperature is 900 ℃, the heating rate and the cooling rate are 2 ℃/min, the heat preservation time is 64h, and the temperature is naturally cooled after being reduced to 700 ℃.
The results of the tests carried out on the materials prepared in the above 10 examples are shown in FIGS. 2 to 6. The results of SEM tests on examples 1,2,5,6,7,9 are shown in FIG. 3, and it can be seen that for Co2+Substituted Ba3(VO4)2The densification temperature of the material is greatly reduced by different proportions; the results of the vibration frequency temperature coefficient and Q f value tests of examples 1 to 10 are shown in fig. 4 and 5, and show that the ceramic obtained a large temperature coefficient of forward resonance frequency (τ f +14.5ppm/° c to +23.8ppm/° c) and a high Q f (25318GHz 54,063 GHz). The substitution amount was used together with Ba obtained in example 62.7Co0.3(VO4)2After the ceramic material is co-fired with the Ag paste, no reaction occurs, and the ceramic material has better matching characteristics, and an SEM image of an interface is shown in figure 7. Using Ba from example 62.7Co0.3(VO4)2The green ceramic chip obtained by casting the ceramic material and the circuit pattern printed by Ag paste on the basis are shown in figures 8 and 9, so that the pattern is good in resolution, the silver seepage phenomenon is avoided, and the problems of the material in the application process of actually manufacturing the LTCC device are well solved.
In conclusion, the present invention is applied to Ba with high microwave dielectric property3(VO4)2Based on that, Co is adopted for the first time2+Substituted Ba3(VO4)2Of Ba2+By using BaCO3CoO and V2O5As raw materials and formula proportion selection, the low-temperature sintering process of the LTCC is realized under the condition of not adopting a sintering reducing agent, and Ba is obtained3(VO4)2The ceramic material has high Q f and large positive value of resonance frequency temperature coefficient (tau f is +14.5 ppm/DEG C to +23.8 ppm/DEG C), so that the ceramic material meets the requirements of the LTCC technical field and has better application prospect.
Claims (1)
1. A Ba-Co-V based low-dielectric low-sintering microwave ceramic material is characterized in that:
has a heightQ*fValue, positiveτfValue of the general chemical formula B3-xCox (VO4)2Wherein x = 0.05-0.5;τfis +14.5 ppm/DEG C to +23.8 ppm/DEG C,Q*f25318 GHz-54,063 GHz;
by using BaCO3CoO and V2O5Is taken as raw material and is mixed according to molar ratio BaCO3：CoO：V2O52.5-2.95: 0.05-0.5: 1, prepared by a solid phase process, wherein BaCO3The molar ratio to CoO is reduced; the presintering temperature in the solid phase method is 700-800 ℃, and the sintering temperature is 900-950 ℃;
the preparation method of the Ba-Co-V based low-dielectric low-sintering microwave ceramic material comprises the following steps:
step 1, mixing the raw material BaCO according to the molar ratio3：CoO：V2O52.5-2.95: 0.05-0.5: 1, preparing the mixture for later use, wherein BaCO is3The molar ratio to CoO is reduced;
step 2, mixing the raw materials prepared in the step 1 according to the following materials: deionized water: the mass ratio of the ball is 1: 1: 1.2-1.5, the rotating speed of the ball mill is 250 r/min-300 r/min, the ball milling time is 6 h-8 h, and the first ball milling is carried out; then drying the mixture at the temperature of between 80 and 120 ℃ and screening the dried mixture by a screen of between 80 and 120 meshes;
step 3, pre-sintering the ball-milling powder obtained in the step 2 at 700-800 ℃, keeping the temperature for 2-3 h, and increasing the temperature at a rate of 1-2 ℃/min;
step 4, mixing the product obtained in the step 3 according to the following materials: deionized water: the mass ratio of the ball is 1: 1: 1.2-1.5, the rotation speed of the ball mill is 250 r/min-300 r/min, and the ball milling time is 8 h-12 h; then drying at 80-120 ℃, adding PVA aqueous solution as a binder for granulation after drying, and performing compression molding at 8-10 MPa for 30-60 s of pressure maintaining time; the PVA aqueous solution accounts for 8-12 wt% of the total mass, and the concentration of the PVA aqueous solution is 5-15 wt%;
step 5, sintering the sample obtained in the step 4 at 900-950 ℃, wherein the heating rate is 1-2 ℃/min, the heat preservation time is 4-6 h, and the positive electrode can be obtained after the sample is naturally cooledτfLow dielectric constant Ba-Co-V base microwave dielectric ceramic material B3-xCox (VO4)2。
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| CN103771842A (en) * | 2014-01-10 | 2014-05-07 | 电子科技大学 | LTCC (Low Temperature Co-fired Ceramics) microwave ceramic material with low cost, low dielectric constant and low loss and preparation method thereof |
| CN107935584A (en) * | 2017-12-12 | 2018-04-20 | 湖南先导电子陶瓷科技产业园发展有限公司 | A kind of microwave dielectric ceramic materials for LTCC and preparation method thereof |
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| CN103771842A (en) * | 2014-01-10 | 2014-05-07 | 电子科技大学 | LTCC (Low Temperature Co-fired Ceramics) microwave ceramic material with low cost, low dielectric constant and low loss and preparation method thereof |
| CN107935584A (en) * | 2017-12-12 | 2018-04-20 | 湖南先导电子陶瓷科技产业园发展有限公司 | A kind of microwave dielectric ceramic materials for LTCC and preparation method thereof |
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Denomination of invention: A Ba Co-V based low dielectric and low firing microwave ceramic material and its preparation method Granted publication date: 20220315 Pledgee: Ganzhou rural commercial bank Limited by Share Ltd. Pledgor: Ganzhou Yanchuang Electronic Technology Co.,Ltd. Registration number: Y2024980002104 |