CN113277848A - Preparation method of intermediate composite vanadate microwave dielectric ceramic - Google Patents
Preparation method of intermediate composite vanadate microwave dielectric ceramic Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910015427 Mo2O3 Inorganic materials 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000013064 chemical raw material Substances 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004891 communication Methods 0.000 abstract description 11
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of a medium composite vanadate microwave dielectric ceramic, which comprises the following main components in chemical formula: LaCu2～x～yCaxMgyVO6(x is more than or equal to 0.0 and less than or equal to 0.3, and y is more than or equal to 0.0 and less than or equal to 0.3); the additive is TiO2The addition amount of the-C composite powder is 5-10 wt%, and the-C composite powder mainly has the following two functions: (1) regulating and controlling the temperature coefficient of the vanadate microwave dielectric ceramic to be nearly zero; the C powder is Mo2O3、Al2O3、WO3、ZrO2At least one of them is selected. The sintering range of the microwave dielectric ceramic is 1200-1300 ℃, the dielectric constant is 15-20, the quality factor Qf is 40000-50000 GHz, the temperature coefficient of the resonance frequency is-10 ppm/DEG C, and the composite vanadate series microwave dielectric ceramic hasThe dielectric constant is moderate, and the excellent dielectric property of the near-zero frequency temperature coefficient is low, so that the requirements of Beidou navigation, satellite communication, Internet of things and 5G communication can be met.
Description
Technical Field
The invention belongs to the technical field of microwave dielectric ceramics, and particularly relates to a preparation method of intermediate composite vanadate series microwave dielectric ceramics.
Background
In recent years, rapid development of Beidou navigation, satellite communication, Internet of things and 5G communication technologies is realized, and high-performance microwave for microwave devices is realizedThe demand of dielectric ceramic materials is also increasing, especially the series ceramics of medium and low dielectric constant, low microwave loss and near zero frequency temperature coefficient. The ceramic can meet the requirements of mobility, portability, miniaturization and miniaturization of communication machines, can meet the requirements of high-performance and high-reliability working characteristics in a microwave range, and is widely concerned. The microwave dielectric material applied to the Beidou navigation, satellite communication, Internet of things and 5G communication technologies has the following basic performance requirements: the temperature coefficient of the resonance frequency is nearly zero, and Qf is more than or equal to 5000 GHz. Newly developed composite vanadate material aCu2VO6The microwave dielectric material has better microwave dielectric property, has the conditions of low quality factor (15000 GHz), overlarge temperature coefficient of resonance frequency (65 ppm/DEG C), poor compactness and the like, and does not meet the application requirements.
Disclosure of Invention
(1) Technical problem to be solved
aCu2VO6Has better microwave dielectric property, but has the problems of low quality factor (15000 GHz), overlarge temperature coefficient of resonance frequency (65 ppm/DEG C), poor compactness and the like, and does not meet the application requirement.
(2) Technical scheme
In order to solve the technical problems, the invention provides a preparation method of a medium composite vanadate-based microwave dielectric ceramic, which comprises the following main components in chemical formula: LaCu2～x～yCaxMgyVO6(x is more than or equal to 0.0 and less than or equal to 0.3, and y is more than or equal to 0.0 and less than or equal to 0.3); the additive is TiO2The addition amount of the-C composite powder is 5-10 wt%, and the-C composite powder mainly has the following two functions: (1) regulating and controlling the temperature coefficient of the vanadate microwave dielectric ceramic to be nearly zero; the C powder is Mo2O3、Al2O3、WO3、ZrO2At least one of the materials is selected to improve the sintering performance of the composite vanadate series microwave dielectric ceramic and reduce microwave loss, and on the other hand, the sintering property and the quality factor can be improved, and the preparation method comprises the following specific steps:
1) the chemical raw material is La2(CO3)3、Cu2(OH)2CO3、V2O5、CaCO3、Mg2(OH)2CO3Respectively according to stoichiometric ratio LaCu2～x～yCaxMgyVO6 (x is more than or equal to 0.0 and less than or equal to 0.3, and y is more than or equal to 0.0 and less than or equal to 0.3) are weighed and mixed;
2) mixing the chemical raw materials prepared in the step 1, putting the mixture into a ball milling tank, and adding zirconia balls and deionized water, wherein the ratio of ball material to water is 1:2.5:3, ball-milling for 14-18 h, placing the ball-milled raw materials in an oven, and drying at 120 ℃;
3) calcining the uniformly mixed powder in the step 2 at the temperature of 1000-1100 ℃ for 3 h;
4) putting the calcined raw materials obtained in the step 3 into a ball milling tank, simultaneously adding 5-10 wt% of additives, adding zirconia balls and deionized water, carrying out ball milling for 20-24 h, drying, adding a PVA solution with the mass solubility of 3% into dried powder as a binder, granulating, and pressing into a cylindrical blank;
5) the cylindrical blank prepared in the step 4 is subjected to heat preservation for 2-4 hours at 1200-1300 ℃ and is sintered into porcelain, and the required low-dielectric microwave dielectric ceramic is obtained;
6) and finally, testing the microwave dielectric property of the low-dielectric microwave dielectric ceramic prepared in the step (5).
And LaCu2～x～yCaxMgyVO6(x is more than or equal to 0.0 and less than or equal to 0.3, and y is more than or equal to 0.0 and less than or equal to 0.3) in La3+、Cu2+And Mg2+Respectively composed of La2(CO3)3、Cu2(OH)2CO3、Mg2(OH)2CO3And (4) introducing. And (3) measuring the microwave dielectric property of the ceramic prepared in the step (5) and the diameter and thickness of the sample by using a micrometer, measuring the dielectric constant of the prepared cylindrical ceramic material by using an Agilent E8363A PNA network analyzer and a Krupka method, putting the test sample into an ESPEC MC-710F type high-low temperature circulating box for measuring the temperature coefficient of the resonant frequency, wherein the temperature range is 20-60 ℃, and the test frequency is 8-14 GHz.
(3) Advantageous effects
The invention has the beneficial effects that: the chemical formula of the inventionIs LaCu2～x～yCaxMgyVO6(0.0≤x≤0.3，0.0≤y≤0.3)+zwt％(TiO2+ C) (z is more than or equal to 5 and less than or equal to 10) composite vanadate series microwave dielectric ceramic material, wherein the sintering range is 1200-1300 ℃, the dielectric constant is 15-20, the quality factor Qf is 40000-50000 GHz, and the temperature coefficient of the resonance frequency is-10 ppm/DEG C. The composite vanadate series microwave dielectric ceramic has excellent dielectric properties of low loss, moderate dielectric constant and near-zero frequency temperature coefficient, and can meet the requirements of Beidou navigation, satellite communication, Internet of things and 5G communication. In addition, the preparation process is simple, pollution-free in process and low in cost, and therefore the preparation method has a wide application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention are further clearly and completely described below with reference to the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example one
This example will be chemical raw material La2(CO3)3、Cu2(OH)2CO3、V2O5、CaCO3、Mg2(OH)2CO3Respectively according to stoichiometric ratio LaCu2～x～yCaxMgyVO6Weighing ingredients (x is 0.2, y is 0.2), mixing, adding the raw materials into a nylon tank, adding zirconia balls and deionized water, ball-milling for 14-18 h at a ball-to-water ratio of 1:2.5:3, placing the ball-milled raw materials into an oven, and drying at 120 ℃; calcining the uniformly mixed powder for 3 hours at 1050 ℃; putting the calcined raw materials into a ball milling tank, and simultaneously adding 8 wt% of TiO2And 1 wt% of Mo2O3、1wt％WO3Adding zirconia balls and deionized water, ball-milling for 20-24 h, drying, adding a PVA solution with the mass solubility of 3% into the dried powder as a binder, granulating, and pressing into a cylindrical blank. The diameter of the embryo body is about 15mm, and the height is about 7.5 mm.
Finally, the cylindrical blank is subjected to heat preservation for 4 hours at 1200-1300 ℃ and sintered into porcelain, and the required composite vanadate microwave dielectric ceramic with low loss, low dielectric constant and near-zero frequency temperature coefficient is obtained; the microwave dielectric property of the composite vanadate microwave dielectric ceramic with low loss, low dielectric constant and near-zero frequency temperature coefficient, which is prepared by a network analyzer and a resonant cavity test, is adopted.
The test results of the relevant process parameters and microwave dielectric properties of the specific example 1 are detailed in the following table 1.1:
table 1.1 test results for relevant process parameters and microwave dielectric properties of example 1
Example two
According to example 1, based on example 1, 0.3 x and 0.3 y are selected, and (8 to t) wt% TiO is added2+twt％(Mo2O3、Al2O3、WO3、ZrO2) Otherwise, the procedure is as in example 1, and the results are shown in Table 1.2.
Table 1.2 test results for relevant process parameters and microwave dielectric properties of example 2
In summary, it can be known from the microwave dielectric property tests of the first and second embodiments that, by substituting CuO with CaO and MgO, on the one hand, the dielectric constant, quality factor and densification characteristic of the composite vanadate-based microwave dielectric ceramic are regulated, and the synthesis temperature is 1000 to 1150 ℃. By TiO2The introduction of the composite vanadate system microwave dielectric ceramic can greatly regulate and control the temperature coefficient of the resonant frequency of the composite vanadate system microwave dielectric ceramic to be close to zero; by adding Mo2O3、Al2O3、WO3、ZrO2At least one of them is selected to improve the quality factor and sintering property.
The chemical formula of the invention is LaCu2～x～yCaxMgyVO6(0.0≤x≤0.3，0.0≤y≤0.3)+zwt％(TiO2+ C) (z is more than or equal to 5 and less than or equal to 10) composite vanadate series microwave dielectric ceramic material, wherein the sintering range is 1200-1300 ℃, the dielectric constant is 15-20, the quality factor Qf is 40000-50000 GHz, and the temperature coefficient of the resonance frequency is-10 ppm/DEG C. The composite vanadate series microwave dielectric ceramic has excellent dielectric properties of low loss, moderate dielectric constant and near-zero frequency temperature coefficient, and can meet the requirements of Beidou navigation, satellite communication, Internet of things and 5G communication.
The above examples are merely representative of preferred embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the present invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (2)
1. A preparation method of intermediate composite vanadate microwave dielectric ceramic is characterized in that the microwave dielectric ceramic mainly comprises the following components in chemical formula: LaCu2～x～yCaxMgyVO6(x is more than or equal to 0.0 and less than or equal to 0.3, and y is more than or equal to 0.0 and less than or equal to 0.3); the additive is TiO2The addition amount of the-C composite powder is 5-10 wt%, and the-C composite powder mainly has the following two functions: (1) regulating and controlling the temperature coefficient of the vanadate microwave dielectric ceramic to be nearly zero; the C powder is Mo2O3、Al2O3、WO3、ZrO2At least one of the materials is selected to improve the sintering performance of the composite vanadate series microwave dielectric ceramic and reduce microwave loss, and on the other hand, the sintering property and the quality factor can be improved, and the preparation method comprises the following specific steps:
1) the chemical raw material is La2(CO3)3、Cu2(OH)2CO3、V2O5、CaCO3、Mg2(OH)2CO3Respectively according to stoichiometric ratio LaCu2～x～yCaxMgyVO6(x is more than or equal to 0.0 and less than or equal to 0.3, and y is more than or equal to 0.0 and less than or equal to 0.3) weighing and batching;
2) mixing the chemical raw materials prepared in the step 1, putting the mixture into a ball milling tank, and adding zirconia balls and deionized water, wherein the ratio of ball material to water is 1:2.5:3, ball-milling for 14-18 h, placing the ball-milled raw materials in an oven, and drying at 120 ℃;
3) calcining the uniformly mixed powder in the step 2 at the temperature of 1000-1100 ℃ for 3 h;
4) putting the calcined raw materials obtained in the step 3 into a ball milling tank, simultaneously adding 5-10 wt% of additives, adding zirconia balls and deionized water, carrying out ball milling for 20-24 h, drying, adding a PVA solution with the mass solubility of 3% into dried powder as a binder, granulating, and pressing into a cylindrical blank;
5) the cylindrical blank prepared in the step 4 is subjected to heat preservation for 2-4 hours at 1200-1300 ℃ and is sintered into porcelain, and the required low-dielectric microwave dielectric ceramic is obtained;
6) and finally, testing the microwave dielectric property of the low-dielectric microwave dielectric ceramic prepared in the step (5).
2. The method as claimed in claim 1, wherein the LaCu is selected from the group consisting of2～x～yCaxMgyVO6(x is more than or equal to 0.0 and less than or equal to 0.3, and y is more than or equal to 0.0 and less than or equal to 0.3) in La3+、Cu2+And Mg2+Respectively composed of La2(CO3)3、Cu2(OH)2CO3、Mg2(OH)2CO3And (4) introducing.
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