CN114075070A - Complex-phase microwave ceramic material, manufacturing method thereof and electronic device - Google Patents
Complex-phase microwave ceramic material, manufacturing method thereof and electronic device Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 120
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000011575 calcium Substances 0.000 claims abstract description 37
- 239000000919 ceramic Substances 0.000 claims abstract description 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 34
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims description 141
- 238000000498 ball milling Methods 0.000 claims description 91
- 239000011777 magnesium Substances 0.000 claims description 67
- 229910052726 zirconium Inorganic materials 0.000 claims description 61
- 238000000227 grinding Methods 0.000 claims description 55
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 32
- 238000007873 sieving Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 24
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 24
- 239000001095 magnesium carbonate Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- 229910052718 tin Inorganic materials 0.000 claims description 21
- 238000005469 granulation Methods 0.000 claims description 20
- 230000003179 granulation Effects 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 17
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000000395 magnesium oxide Substances 0.000 claims description 14
- 229910052758 niobium Inorganic materials 0.000 claims description 14
- 229910052715 tantalum Inorganic materials 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 229910019653 Mg1/3Nb2/3 Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 229910002971 CaTiO3 Inorganic materials 0.000 abstract description 40
- 239000002131 composite material Substances 0.000 abstract description 12
- 239000002002 slurry Substances 0.000 description 60
- 239000010936 titanium Substances 0.000 description 42
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 40
- 239000010955 niobium Substances 0.000 description 38
- 239000000843 powder Substances 0.000 description 27
- 239000011701 zinc Substances 0.000 description 25
- 229910052909 inorganic silicate Inorganic materials 0.000 description 23
- 239000004677 Nylon Substances 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 238000003801 milling Methods 0.000 description 20
- 229920001778 nylon Polymers 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 229910052839 forsterite Inorganic materials 0.000 description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 229910017676 MgTiO3 Inorganic materials 0.000 description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000004891 communication Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- 238000012986 modification Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910002976 CaZrO3 Inorganic materials 0.000 description 3
- 229910002244 LaAlO3 Inorganic materials 0.000 description 3
- 229910003080 TiO4 Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 230000010267 cellular communication Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
The embodiment of the application provides a complex-phase microwave ceramic material, a manufacturing method thereof and an electronic device. By the reaction of CaTiO3Both Ca and Ti in the calcium carbonate are modified, or CaTiO is modified3Ti in the microwave ceramic material is modified, so that the dielectric constant of the formed microwave ceramic material is less than or equal to 22, and the absolute delta f/f is within a wide temperature range of-40 to 110 DEG C25℃|<400ppm and a high Qf value (>40THz), therefore, the complex phase microwave ceramic material provided by the embodiment of the application is a microwave dielectric ceramic material with low resonant frequency temperature coefficient in a wide temperature region, and meets the requirements of low resonant frequency temperature coefficient and low frequency drift (namely, low resonant frequency temperature coefficient and low frequency drift) expected for the microwave dielectric ceramic<400ppm) and a high Qf value (>40THz), solves the existing MgTiO3‑CaTiO3The composite ceramic has the problems of large vf and high frequency drift in a wide temperature range of-40 to 25 ℃.
Description
Technical Field
The embodiment of the application relates to the technical field of ceramics, in particular to a complex-phase microwave ceramic material, a manufacturing method thereof and an electronic device.
Background
With the continuous progress of communication technology, especially the modern communication such as mobile communication, satellite communication, global positioning satellite system (GPS, bluetooth technology and wireless local area network) is rapidly developed, and the microwave dielectric ceramic device is very useful for the application in the communication field due to the extremely high frequency, extremely short wavelength, large information capacity, strong directivity, penetrability and absorption capability of microwave signals, so the demand for high-performance and high-quality microwave dielectric device materials is increasing day by day, for example, microwave base station transmitters, receivers and mobile phones in the GSM cellular communication system need a large amount of microwave dielectric ceramic materials such as resonators, filters, oscillators, dielectric antennas, etc., and the microwave dielectric ceramic has higher dielectric constant, which is more beneficial for the small volume, high performance and light weight of the filters, and the dielectric ceramic material has high Q (quality factor) value, when the microwave dielectric ceramic is applied to microwave communication devices such as dielectric resonators, dielectric combiners, dielectric antennas and the like, the miniaturization and low cost of wireless communication equipment are realized, and therefore, the microwave dielectric ceramic is a key basic material for preparing electronic components for communication.
At present, MgO-TiO is commonly used as microwave dielectric ceramic2System ceramics, mainly Mg2TiO4Or MgTiO3As the first phase material, CaTiO is adopted3The material is a normal-temperature phase-shifting material, and MgTiO with a composite structure is prepared from a first-phase material and the normal-temperature phase-shifting material3-CaTiO3Composite ceramics.
However, MgTiO prepared as described above3-CaTiO3In the composite ceramic, the temperature coefficient of the resonance frequency within 25-85 ℃ can be within-3 ppm/DEG C, and the absolute value of the frequency drift can be realized<200ppm, the product of Q value and resonance frequency (Qf) of the material is about 45THz, the dielectric constant is 19.5, but the absolute value of frequency drift is above 13 ppm/DEG C at-40-25 ℃ and the temperature coefficient of resonance frequency>850ppm, which can not satisfy the requirements of low temperature coefficient of resonance frequency (i.e. + -. 3 ppm/DEG C) and low frequency drift (i.e. + -. 3 ppm/DEG C) for microwave dielectric ceramics<400ppm) and high Qf values (i.e.>40THz)。
Disclosure of Invention
The embodiment of the application provides a complex-phase microwave ceramic material, a manufacturing method thereof and an electronic device, which reduces the dielectric constant of the microwave ceramic material, ensures low frequency drift and low resonant frequency temperature coefficient in a wide temperature region, realizes a high Qf value of the microwave ceramic material, and solves the problem that the existing microwave ceramic material cannot meet the requirements of the microwave dielectric ceramic on the low resonant frequency temperature coefficient, the low frequency drift and the high Qf value.
The first aspect of the embodiments of the present application provides a complex-phase microwave ceramic material, which comprises the following main components:
a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4
wherein the content of the first and second substances,
a is at least one of Ca, RE and Sr, wherein RE is a rare earth element and at least contains La;
the B is at least one of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr and Ga, and when the A is Ca or Sr, the B is one or more of Sn and Zr, and when the A is Ca or Sr, the B is Mg1/3Nb2/3,Zn1/3Nb2/3,Al1/2Nb1/2,Ga1/ 2Nb1/2When said a is RE, said B is one or more of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr;
c is Mg1-m-n-qZnmConNiqM is more than or equal to 0 and less than or equal to 0.3, n is more than or equal to 0 and less than or equal to 0.3, and q is more than or equal to 0 and less than or equal to 0.3;
d is Ti1-t-wSntZrwT is more than or equal to 0 and less than or equal to 0.1, and w is more than or equal to 0 and less than or equal to 0.1;
e is SirGe1-rAnd r is more than or equal to 0.7 and less than or equal to 1;
a is more than or equal to 0 and less than or equal to 0.95, b is more than or equal to 0.95, c is more than or equal to 0.05 and less than or equal to 0.4, d is more than or equal to 0 and less than or equal to 0.8, a + b + c + d is 1, x is more than 0.05 and less than or equal to 0.7, and y is more than or equal to 0 and less than or equal to 0.35.
The complex phase microwave ceramic material provided by the embodiment of the application is prepared by adding CaTiO3Both Ca and Ti in the solution are modified (e.g. to CaTiO)3Both A and B in (A) or to CaTiO3Ti (e.g. CaTiO)3In (B) positionLine substitution) is carried out, the dielectric constant of the formed microwave ceramic material is less than or equal to 22, and the absolute delta f/f is within a wide temperature range of minus 40 to 110 DEG C25℃|<400ppm and a high Qf value (Qf value)>40THz), therefore, the complex phase microwave ceramic material provided by the embodiment of the application is a microwave dielectric ceramic material with a low resonant frequency temperature coefficient in a wide temperature region, and meets the requirements of the microwave dielectric ceramic for a low resonant frequency temperature coefficient (i.e., +/-3 ppm/DEG C) and a low frequency drift (i.e., + -3 ppm/DEG C)<400ppm) and high Qf values (i.e.>40THz), solves the existing MgTiO3-CaTiO3The composite ceramic has the problems of large vf and high frequency drift in a wide temperature range of-40 to 25 ℃.
A second aspect of the embodiments of the present application provides a method for manufacturing a complex-phase microwave ceramic material, the method comprising the following steps:
according to a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4CO and DO in the component2、CaO、TiO2、ApOq、BsOw、MgO、EO2Weighing the following raw materials in a molar ratio: one of CO, C carbonate and C basic carbonate and DO2Calcium carbonate, TiO2、ApOq、BsOw、MgO、EO2；
Mixing the raw materials, performing ball milling, drying and sieving the ball-milled mixture, and pre-sintering at 900-1400 ℃ for 2-10 hours to obtain a pre-sintered material;
finely grinding and drying the pre-sintered material, mixing the pre-sintered material with a binder solution, and granulating, wherein the granulation size D50 is 40-100 um;
putting the granules obtained by granulation into a forming grinding tool for dry pressing and forming to obtain a green body;
sintering the green body at 1250-1500 ℃ for 1.5-6 h to obtain the complex-phase microwave dielectric ceramic material;
a is at least one of Ca, RE and Sr, wherein RE is a rare earth element and at least contains La;
b isAt least one of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr and Ga, and when the A is Ca or Sr, the B is one or more of Sn and Zr, and when the A is Ca or Sr, the B is Mg1/3Nb2/3,Zn1/3Nb2/3,Al1/2Nb1/2,Ga1/ 2Nb1/2When said a is RE, said B is one or more of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr;
c is Mg1-m-n-qZnmConNiqM is more than or equal to 0 and less than or equal to 0.3, n is more than or equal to 0 and less than or equal to 0.3, and q is more than or equal to 0 and less than or equal to 0.3;
d is Ti1-t-wSntZrwT is more than or equal to 0 and less than or equal to 0.1, and w is more than or equal to 0 and less than or equal to 0.1;
e is SirGe1-rAnd r is more than or equal to 0.7 and less than or equal to 1;
a is more than or equal to 0 and less than or equal to 0.95, b is more than or equal to 0.95, c is more than or equal to 0.05 and less than or equal to 0.4, d is more than or equal to 0 and less than or equal to 0.8, a + b + c + d is 1, x is more than 0.05 and less than or equal to 0.7, and y is more than or equal to 0 and less than or equal to 0.35;
q, p, s and w are positive integers.
A third aspect of the embodiments of the present application provides a method for manufacturing a complex-phase microwave ceramic material, including the following steps:
according to a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Middle CO and DO2Weighing the following raw materials in a molar ratio: one of CO, C carbonate and C basic carbonate and DO2Mixing the raw materials, ball-milling, drying, sieving, and presintering at 900-1400 ℃ for 2-10 h to obtain CDO3And C2DO4；
According to a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Medium CaO, TiO2、ApOq、BsOwWeighing the following raw materials in a molar ratio: calcium carbonate, TiO2、ApOq、BsOwAnd mixing calcium carbonate and TiO2、ApOq、BsOwBall-milling, drying, sieving, and presintering at 900-1400 deg.C for 2-10 h to obtain (1-x) CaTiO3–x A1-yBO3；
According to a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Medium MgO, EO2Weighing raw materials in a molar ratio: one of MgO, magnesium carbonate and basic magnesium carbonate and EO2And mixing EO2And MgO or magnesium carbonate or basic magnesium carbonate are subjected to ball milling, drying and sieving, and then are presintered for 2-10 hours at the temperature of 900-1400 ℃ to prepare Mg2EO4；
A CDO3、b C2DO4、c((1-x)CaTiO3–x A1-yBO3) And d Mg2EO4Mixing, performing ball milling, drying, mixing with a binder solution, and granulating, wherein the granulation size D50 is 40-100 um;
putting the granules obtained by granulation into a forming grinding tool for dry pressing and forming to obtain a green body;
sintering the green body at 1250-1500 ℃ for 1.5-6 h to obtain the complex-phase microwave dielectric ceramic material;
a is at least one of Ca, RE and Sr, wherein RE is a rare earth element and at least contains La;
the B is at least one of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr and Ga, and when the A is Ca or Sr, the B is one or more of Sn and Zr, and when the A is Ca or Sr, the B is Mg1/3Nb2/3,Zn1/3Nb2/3,Al1/2Nb1/2,Ga1/ 2Nb1/2When said a is RE, said B is one or more of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr;
c is Mg1-m-n-qZnmConNiqM is more than or equal to 0 and less than or equal to 0.3, n is more than or equal to 0 and less than or equal to 0.3 and 0≤q≤0.3；
D is Ti1-t-wSntZrwT is more than or equal to 0 and less than or equal to 0.1, and w is more than or equal to 0 and less than or equal to 0.1;
e is SirGe1-rAnd r is more than or equal to 0.7 and less than or equal to 1;
a is more than or equal to 0 and less than or equal to 0.95, b is more than or equal to 0.95, c is more than or equal to 0.05 and less than or equal to 0.4, d is more than or equal to 0 and less than or equal to 0.8, a + b + c + d is 1, x is more than 0.05 and less than or equal to 0.7, and y is more than or equal to 0 and less than or equal to 0.35;
q, p, s and w are positive integers.
A fourth aspect of the embodiments of the present application provides an electronic device, including at least: the microwave ceramic part is made of the complex phase microwave ceramic material, or the microwave ceramic part is made of the complex phase microwave ceramic material prepared by any one of the above manufacturing methods.
Detailed Description
The terminology used in the description of the embodiments section of the present application is for the purpose of describing particular embodiments only, and is not intended to be limiting of the application, of which embodiments will be described in detail below.
Definition of terms:
temperature coefficient of resonance frequency vf is 1/f25℃X (Δ f/Δ T), wherein f25℃Is the resonance frequency at 25 deg.C and Δ T is the temperature change.
Δf/f25℃Is the frequency drift, defined as the ratio of the change in resonant frequency relative to 25 ℃ to the resonant frequency at 25 ℃, Δ f/f25℃The value is negative, indicating a shift of the resonance frequency to low frequencies, Δ f/f, relative to 25 deg.C25℃Values are positive to indicate that the resonant frequency shifts towards higher frequencies relative to 25 ℃.
And Qf: the product of the Q value (quality factor) of the material and the resonance frequency (f).
With the development of communication technology, the requirements for electronic components made of microwave ceramic materials are higher and higher, so that higher requirements are put on the performance of the microwave ceramic materials, for example, the parameters of the desired microwave ceramic materials are as follows: dielectric constant (less than or equal to 22)High Qf value (>40THz) and a low temperature coefficient of resonance frequency vf in a wide temperature range. For example, it is desirable that vf be within. + -. 3 ppm/DEG C over a wide temperature range of-40 ℃ to 125 ℃. In addition, a wide temperature range of-40 to 125 ℃ is required25℃|<400ppm。
MgO-TiO is commonly used as microwave ceramic material2System ceramics, MgO-TiO2The system ceramic mainly adopts two structures with high Qf values: mg (magnesium)2TiO4，MgTiO3Wherein, MgO-TiO2The material has a negative vf of about-50 ppm/DEG C, a dielectric constant of 14-17, and a Qf greater than 250THz, wherein to achieve a vf close to zero, a material having a positive vf is typically used, such as CaTiO3，CaTiO3The vf of (A) is 800 ppm/DEG C, the dielectric constant is 180, and the Qf value is about 10000 GHz. By CaTiO3For MgO-TiO2Adjusting parameters of the system ceramic, wherein, CaTiO3With MgO-TiO2The system ceramic forms MgTiO with composite phase structure3-CaTiO3Composite ceramics.
Wherein 5 mol% of CaTiO is adopted3And 95 mol% of MgTiO3The ceramic material formed by compounding is obtained by testing: vf is-3 to 3 ppm/DEG C and delta f/f within 25 to 85 DEG C25℃|<200ppm, Qf about 45THz, and a dielectric constant of 19.5, but vf is above 13 ppm/DEG C within-40 to 25 |. DELTA.f/f25℃|>850 ppm. Therefore, the above composite ceramic material can not meet the requirements of the required microwave ceramic material (i.e. vf is + -3 ppm/DEG C in the wide temperature range of-40 to 125℃, and | delta f/f in the wide temperature range of-40 to 125℃)25℃|<400ppm, density<4.0g/cm3)。
For this purpose, for CaTiO3The modification can reduce the change of dielectric constant with temperature and realize the improvement of temperature drift, for example, CaTiO is commonly adopted in the industry3In which Ca is substituted by rare-earth elements, e.g. Sm for CaTiO3Partial replacement of Ca in the magnesium-calcium alloy with MgTiO3The molecular formula of the ceramic material formed after compounding is as follows: (1-x1) MgTiO3-x1(Ca1-y1 Smy1)TiO30.03 ≦ x1 ≦ 0.15, 0.001 ≦ y1 ≦ 0.06, and the ceramic material formed was found to be CaTiO, measured3In (1)When a small amount of Ca is substituted, the Qf value of the ceramic material can be improved, the temperature drift is slightly improved, but vf is low-temperature section>10 ppm/DEG C, when the Ca substitution amount is large, the Qf value deteriorates seriously, and Qf<30THz, and in addition, the density of elements such as rare earth Sm, Nd and the like is high, so that the product application cannot be met.
To solve the problems of the above pair of CaTiO3The embodiment of the application provides a complex phase microwave ceramic material, aiming at the problems of contradiction between Qf, low temperature drift and density in modification3In which both Ca and Ti are modified, e.g. CaTiO3In which both Ca and Ti are substituted, or to CaTiO3Modification of Ti in (1), e.g. CaTiO3The molecular formula of the main component compound of the formed microwave ceramic material is as follows: a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4By the pair of CaTiO3The A, B bit or B bit in the ceramic material is replaced to ensure that the positive temperature drift material has high Qf value, low density and low temperature drift, the dielectric constant of the formed complex phase ceramic microwave ceramic material is less than or equal to 22, and the absolute delta f/f is within a wide temperature range of minus 40 to 110 DEG C25℃|<400ppm, high Qf value (Qf value)>40THz) and low density, and therefore, the microwave ceramic material provided by the embodiment of the application meets the requirements of low resonant frequency temperature coefficient and low frequency drift (namely, low frequency drift) expected for microwave dielectric ceramics<400ppm), low density, and high Qf value (i.e.>40THz), solves the existing MgTiO3-CaTiO3The composite ceramic has the problems of large vf and high frequency drift in a wide temperature range of-40 to 25 ℃.
The components are main effective components of the microwave dielectric ceramic material product, and additives added in the preparation process and trace physical impurities contained in the raw materials or generated in the preparation process are not included.
The specific composition of the microwave ceramic material provided in the embodiments of the present application is described in detail below.
The microwave ceramic material provided by the embodiment at least comprises: negative temperature drift phase material and positive temperature drift phase material, wherein, the negative temperature drift phase materialIs a CDO3–b C2DO4And Mg2EO4The normal temperature drift phase material is (1-x) CaTiO3–x A1-yBO3I.e. examples of this application, to CaTiO3The Ca and the Ti are modified or the Ti is modified to form CaTiO with the molecular formula of (1-x)3–x A1-yBO3The compound is used as a positive temperature drift material.
Wherein the molecular formula of the compound consisting of the negative temperature drift phase material and the positive temperature drift phase material is a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4That is, in the embodiment of the present application, the molecular formula of the microwave ceramic material is a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4. a. b, c, d, x and y are molar ratios, a is more than or equal to 0 and less than or equal to 0.95, b is more than or equal to 0 and less than or equal to 0.95, and c is more than or equal to 0.05 and less than or equal to 0.95<0.4，0≤d<0.8，a+b+c+d＝1，0.05<x≤0.7,0≤y≤0.35。
Wherein A is at least one of Ca, RE and Sr, RE is a rare earth element and at least contains a low-density rare earth element La; b is at least one of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr and Ga;
and when A is Ca or Sr, B is one or more of Sn and Zr, and a plurality of them are mixed in an arbitrary ratio, for example, CaTiO3In which Ca (i.e. A site) is not substituted, to CaTiO3Replacing Ti (namely B site) in the titanium oxide with Zr to form a positive temperature drift material (1-x) CaTiO3-xCaZrO3；
When A is Ca or Sr, B can also be Mg1/3Nb2/3,Zn1/3Nb2/3,Al1/2Nb1/2,Ga1/2Nb1/2And a plurality thereof may be mixed in an arbitrary ratio, for example, CaTiO3In which Ca (i.e. A site) is not substituted, to CaTiO3Al for Ti (i.e. B site) in1/2Nb1/2Or Zn1/3Nb2/3The positive temperature drift material (1-x) CaTiO3-xCa (Al) is formed1/2Nb1/2) O3 or (1-x) CaTiO3-xCa(Zn1/3Nb2/3)O3；
When A is RE, B is one or more of Ti, Sn, Al, Mg, Zn, Nb, Ta and Zr, and a plurality of B can be mixed according to any proportion, namely CaTiO3Both Ca and Ti in the solution are substituted (namely, CaTiO)3All A, B in the formula) can be modified, for example, the positive temperature drift material can be (1-x) CaTiO3-xLaAlO3(1-x) CaTiO3-xLa (Mg1/2Ti1/2) O3, etc.;
the microwave ceramic material provided by the embodiment of the application comprises a negative temperature drift phase material and a positive temperature drift phase material, wherein the positive temperature drift phase material is a para-CaTiO3Chemical species modified at position A, B or B: (1-x) CaTiO3–x A1-yBO3Thus, the positive temperature drift material formed by modification is combined with CaTiO alone3Compared with the material, the positive temperature drift phase material formed by modification can realize high Qf value, low temperature drift and low density, thus ensuring that the formed microwave ceramic material has high Qf value, low temperature drift and low density in a wide temperature range (such as-40-110 ℃).
Wherein, in the embodiment of the application, C is Mg1-m-n-qZnmConNiqM is more than or equal to 0 and less than or equal to 0.3, n is more than or equal to 0 and less than or equal to 0.3, and q is more than or equal to 0 and less than or equal to 0.3; d is Ti1-t-wSnt ZrwT is more than or equal to 0 and less than or equal to 0.1, and w is more than or equal to 0 and less than or equal to 0.1; e is SirGe1-rAnd r is more than or equal to 0.7 and less than or equal to 1;
in one possible implementation, C is Mg, D is Ti, and E is Si, for example, the microwave dielectric material has a molecular formula of a MgTiO3–b Mg2TiO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2SiO4。
In the examples of the present application, Mg2EO4The negative temperature drift phase has a low dielectric constant, so that the dielectric constant of the microwave ceramic material can be adjusted by including a low-dielectric negative temperature drift material, so that the dielectric constant of the microwave ceramic material formed by compounding the positive and negative temperature drift materials can be adjusted to be less than or equal to 22 (see table 1 below for details), and if MgTiO is adopted3-CaTiO3(and rare earth elements Sm and Nd for Ca at A siteSubstituted) -Mg2SiO4When the three-phase material is compounded to form the microwave ceramic material, the dielectric constant of the microwave ceramic material can be reduced, but the Qf value of the microwave ceramic material is low.
In the present embodiment, a CDO is used3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4When the composite microwave ceramic material is formed, the positive temperature phase-shifting material is (1-x) CaTiO3–x A1-yBO3To CaTiO3Is substituted at the A site, the B site or the B site, so that the positive temperature drift phase material has high Qf value, low temperature drift and low density, and Mg2EO4The phase has low dielectric constant, so that the microwave ceramic material finally formed by compounding has high Qf value (namely more than 40THz), low density and low dielectric constant (namely the dielectric constant is less than or equal to 22).
The preparation method of the complex-phase microwave ceramic material provided by the embodiment of the present application is described in detail below with reference to the embodiments.
Example one
The molecular formula of the microwave ceramic material provided by the embodiment of the application is as follows: a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Wherein A is1-yBO3Is LaAlO3B is 0, C is Mg, D is Ti, E is Si, that is, the molecular formula of the microwave ceramic material is: alpha MgTiO3–c((1-x)CaTiO3–x LaAlO3)–d Mg2SiO4. Namely pair CaTiO3The A site (Ca) and the B site (Ti) are replaced, and the positive temperature drift material is (1-x) CaTiO3–x LaAlO3The negative temperature drift phase material is MgTiO3And Mg2SiO4。
Wherein a may be 0.69, c may be 0.16, d may be 0.15, and x may be 0.2, so in the embodiment of the present application, the molecular formula of the microwave ceramic material is 0.69MgTiO3-0.16(0.8CaTiO3–0.2LaAlO3)-0.15Mg2SiO4Wherein the preparation molecular formula is 0.69MgTiO3-0.16(0.8CaTiO3–0.2LaAlO3)-0.15Mg2SiO4The microwave ceramic material can be prepared by two methods:
the method comprises the following steps: negative temperature drift phase materials can be prepared respectively: MgTiO 23And positive temperature phase-shifting material: 0.8CaTiO3–0.2LaAlO3Negative temperature drift phase material: mg (magnesium)2SiO4。
Wherein MgTiO is prepared3According to MgTiO3Medium MgO, TiO2Respectively weighing magnesium oxide, magnesium carbonate or basic magnesium carbonate and TiO according to the molar content2Wherein, in the examples of the present application, basic magnesium carbonate (analytically pure) and TiO are specifically weighed2Then adding basic magnesium carbonate and TiO2Mixing and placing the mixture in a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding materials and the zirconium balls in a ratio of 1:5, carrying out primary ball milling for 8 hours, taking out slurry after the ball milling, drying the slurry for 4 hours at 120 ℃, sieving the slurry by a 40-mesh sieve to obtain primary ball grinding material, and presintering the sieved ball grinding material for 6 hours at 1250 ℃ to obtain MgTiO3。
Preparation of 0.8CaTiO3–0.2LaAlO3According to 0.8CaTiO3–0.2LaAlO3Medium CaO, TiO2Lanthanum oxide (La)2O3)、Al2O3Weighing the following raw materials in molar content: TiO 22、La2O3Calcium carbonate, Al2O3Adding TiO to2、La2O3Calcium carbonate, Al2O3Mixing and placing the mixture in a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding materials and the zirconium balls in a ratio of 1:5, carrying out primary ball milling for 8 hours, taking out the slurry after the ball milling, drying the slurry for 4 hours at 120 ℃, sieving the slurry by a 40-mesh sieve to obtain a primary ball grinding material, and presintering the sieved ball grinding material for 6 hours at 1250 ℃ to obtain 0.8CaTiO3–0.2LaAlO3。
Preparation of Mg2SiO4According to Mg2SiO4Medium MgO, SiO2Weighing the following raw materials in molar content: siO2And magnesium oxide or magnesium carbonate or basic magnesium carbonate (analytically pure), in the embodiment of the application, the raw materials to be weighed are basic magnesium carbonate and SiO2Basic magnesium carbonate and SiO2Mixing and placing the mixture in a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding materials and the zirconium balls in a ratio of 1:5, carrying out primary ball milling for 8 hours, taking out slurry after ball milling, drying the slurry for 4 hours at 120 ℃, sieving the slurry by a 40-mesh sieve to obtain primary ball grinding material, and presintering the sieved ball grinding material for 6 hours at 1250 ℃ to obtain Mg2SiO4。
According to the molar ratio of the three phases, a (namely 0.69), c (namely 0.16) and d (namely 0.15), 0.69MgTiO is added3、0.16(0.8CaTiO3–0.2LaAlO3)、0.15Mg2SiO4Mixing and putting into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding materials and the zirconium balls in a ratio of 1:5 to perform secondary ball milling for 6 hours; after ball milling, taking out the slurry, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain a secondary ball grinding material; adding PVA (polyvinyl alcohol) which is 5 wt% of the secondary ball grinding material into the secondary ball grinding material for granulation, controlling the D50 of the size of the granulation powder to be about 80 mu m, putting the granulation powder into a die with the diameter of 12.5mm, and pressing the granulation powder into a green body with the diameter of 12.5mm multiplied by 6mm under 200 MPa; and (3) sintering the green body in the air at the temperature of 1360 ℃ for 4 hours to obtain the complex-phase microwave dielectric ceramic material: 0.69MgTiO3-0.16(0.8CaTiO3–0.2LaAlO3)-0.15Mg2SiO4。
The method 2 comprises the following steps: according to 0.69MgTiO3-0.16(0.8CaTiO3–0.2LaAlO3)-0.15Mg2SiO4The molar content ratio of each compound in the formula (I) is measured by weighing basic magnesium carbonate (analytically pure), calcium carbonate (analytically pure), lanthanum oxide (analytically pure) and SiO2Mixing (analytically pure), aluminum oxide (analytically pure) and titanium oxide (analytically pure) as raw materials, putting the prepared mixture into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, adding materials and the zirconium balls in a ratio of 1:5, and carrying out primary ball milling for 8 hours;and (4) taking out the slurry after ball milling, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain the primary ball grinding material. And pre-burning the primary ball grinding material for 6 hours at the temperature of 1250 ℃ to obtain the pre-sintered material. Putting the pre-sintered material into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding the material and the zirconium balls at a ratio of 1:5 to perform secondary ball milling for 6 hours; after ball milling, taking out the slurry, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain a secondary ball grinding material; adding PVA (polyvinyl alcohol) which accounts for 5 wt% of the mass of the secondary ball grinding material into the secondary ball grinding material for granulation, controlling the D50 of the size of the granulated powder to be about 80 mu m, putting the granulated powder into a die with the diameter of 12.5mm, and pressing the granulated powder into a green body with the diameter of 12.5mm multiplied by 6mm under 200 MPa; and (3) sintering the green body in air at a temperature of 1380 ℃ for 4 hours to obtain the complex-phase microwave dielectric ceramic material: 0.69MgTiO3-0.16(0.8CaTiO3–0.2LaAlO3)-0.15Mg2SiO4。
Example two
The molecular formula of the microwave ceramic material provided by the embodiment of the application is as follows: a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Wherein A is1-yBO3Is La (Mg)1/2Ti1/2)O3The formula of the microwave ceramic material provided by the embodiment of the present application is as follows: alpha MgTiO3–c((1-x)CaTiO3–x La(Mg1/2Ti1/2)O3)-d Mg2SiO4. Namely pair CaTiO3The A site (Ca) and the B site (Ti) are both substituted, and the positive temperature drift material is (1-x) CaTiO3–x La(Mg1/2Ti1/2)O3The negative temperature drift phase material is MgTiO3And Mg2SiO4。
In this embodiment, a may be 0.70, c may be 0.15, d may be 0.15, and x may be 0.2, so that in this embodiment, the molecular formula of the microwave ceramic material is 0.70MgTiO3-0.15(0.8CaTiO3–0.2La(Mg1/ 2Ti1/2)O3)-0.15Mg2SiO4Wherein the preparation molecular formula is 0.70MgTiO3-0.15(0.8CaTiO3–0.2La(Mg1/ 2Ti1/2)O3)-0.15Mg2SiO4The microwave ceramic material of (1) can be prepared by two methods in the first embodiment, in the embodiment of the present application, the method 2 in the first embodiment is specifically taken as an example to prepare a microwave ceramic material, and the specific preparation method is as follows:
according to 0.70MgTiO3-0.15(0.8CaTiO3–0.2La(Mg1/2Ti1/2)O3)-0.15Mg2SiO4Weighing basic magnesium carbonate (analytically pure), calcium carbonate (analytically pure), lanthanum oxide (analytically pure), SiO2 (analytically pure) and titanium oxide (analytically pure) as raw materials, mixing, putting the prepared mixture into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, adding materials and the zirconium balls in a ratio of 1:5, and performing primary ball milling for 8 hours; and (4) taking out the slurry after ball milling, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain the primary ball grinding material. And pre-burning the primary ball grinding material for 6 hours at the temperature of 1200 ℃ to obtain a pre-burnt material. Putting the pre-sintered material into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding the material and the zirconium balls at a ratio of 1:5 to perform secondary ball milling for 6 hours; after ball milling, taking out the slurry, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain a secondary ball grinding material; adding PVA (polyvinyl alcohol) which accounts for 5 wt% of the mass of the secondary ball grinding material into the secondary ball grinding material for granulation, controlling the D50 of the size of the granulated powder to be about 80 mu m, putting the granulated powder into a die with the diameter of 12.5mm, and pressing the granulated powder into a green body with the diameter of 12.5mm multiplied by 6mm under 200 MPa; and (3) sintering the green body in air at a temperature of 1380 ℃ for 4 hours to obtain the complex-phase microwave dielectric ceramic material: 0.70MgTiO3-0.15(0.8CaTiO3–0.2La(Mg1/2Ti1/2)O3)-0.15Mg2SiO4。
EXAMPLE III
The molecular formula of the microwave ceramic material provided by the embodiment of the application is：a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Wherein A is1-yBO3Is Ca (Al)1/2Nb1/2)O3The formula of the microwave ceramic material provided by the embodiment of the present application is as follows: alpha MgTiO3–c((1-x)CaTiO3–x Ca(Al1/2Nb1/2)O3)-d Mg2SiO4. Namely pair CaTiO3The B site (namely Ti) is substituted, and the positive temperature phase-shifting material is (1-y) CaTiO3–y Ca(Al1/2Nb1/2)O3The negative temperature drift phase material is MgTiO3And Mg2SiO4。
In this embodiment, a may be 0.65, c may be 0.19, d may be 0.16, and x may be 0.2, so that in this embodiment, the molecular formula of the microwave ceramic material is 0.65MgTiO3-0.19(0.8CaTiO3–0.2Ca(Al1/ 2Nb1/2)O3)-0.16Mg2SiO4Wherein the preparation molecular formula is 0.65MgTiO3-0.19(0.8CaTiO3–0.2Ca(Al1/ 2Nb1/2)O3)-0.16Mg2SiO4The microwave ceramic material of (1) can be prepared by two methods in the first embodiment, in the embodiment of the present application, the method 2 in the first embodiment is specifically taken as an example to prepare a microwave ceramic material, and the specific preparation method is as follows:
according to 0.65MgTiO3-0.19(0.8CaTiO3–0.2Ca(Al1/2Nb1/2)O3)-0.16Mg2SiO4The molar content ratio of each compound in the formula (I) is measured by weighing basic magnesium carbonate (analytically pure), calcium carbonate (analytically pure), alumina (analytically pure), niobium pentoxide (analytically pure), and SiO2Mixing (analytically pure) and titanium oxide (analytically pure) as raw materials, putting the prepared mixture into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, adding materials and the zirconium balls in a ratio of 1:5, and carrying out primary ball milling for 8 hours; ball milling is finishedAnd taking out the slurry, drying the slurry for 4 hours at the temperature of 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain the primary ball grinding material. And pre-burning the primary ball grinding material for 6 hours at the temperature of 1200 ℃ to obtain a pre-burnt material. Putting the pre-sintered material into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding the material and the zirconium balls at a ratio of 1:5 to perform secondary ball milling for 6 hours; after ball milling, taking out the slurry, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain a secondary ball grinding material; adding PVA (polyvinyl alcohol) which accounts for 5 wt% of the mass of the secondary ball grinding material into the secondary ball grinding material for granulation, controlling the D50 of the size of the granulated powder to be about 80 mu m, putting the granulated powder into a die with the diameter of 12.5mm, and pressing the granulated powder into a green body with the diameter of 12.5mm multiplied by 6mm under 200 MPa; and (3) sintering the green body in air at the temperature of 1400 ℃ for 4 hours to obtain the final microwave dielectric ceramic material: 0.65MgTiO3-0.19(0.8CaTiO3–0.2Ca(Al1/2Nb1/2)O3)-0.16Mg2SiO4。
Example four
The molecular formula of the microwave ceramic material provided by the embodiment of the application is as follows: a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Wherein A is1-yBO3Is CaZrO3The formula of the microwave ceramic material provided by the embodiment of the present application is as follows: alpha MgTiO3–c((1-x)CaTiO3–x CaZrO3). Namely pair CaTiO3The B site (namely Ti) is substituted, and the positive temperature phase-shifting material is (1-x) CaTiO3–x CaZrO3The negative temperature drift phase material is MgTiO3。
In this embodiment, a may be 0.79, c may be 0.21, and x may be 0.7, so that in this embodiment, the molecular formula of the microwave ceramic material is 0.79MgTiO3-0.21(0.3CaTiO3–0.7CaZrO3) Wherein the preparation molecular formula is 0.79MgTiO3-0.21(0.3CaTiO3–0.7CaZrO3) The microwave ceramic material can be prepared by adopting two methods in the first embodiment, and the application is thatIn the embodiment, the method 2 in the first embodiment is specifically taken as an example to prepare the microwave ceramic material, and the specific preparation method is as follows:
according to 0.79MgTiO3-0.21(0.3CaTiO3–0.7CaZrO3) Weighing basic magnesium carbonate (analytically pure), calcium carbonate (analytically pure), zirconium oxide (analytically pure) and titanium oxide (analytically pure) as raw materials, mixing, putting the prepared mixture into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and carrying out primary ball milling for 8 hours, wherein the ratio of the added materials to the zirconium balls is 1: 5; and (4) taking out the slurry after ball milling, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain the primary ball grinding material. And pre-burning the primary ball grinding material for 6 hours at the temperature of 1200 ℃ to obtain a pre-burnt material. Putting the pre-sintered material into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding the material and the zirconium balls at a ratio of 1:5 to perform secondary ball milling for 6 hours; after ball milling, taking out the slurry, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain a secondary ball grinding material; adding PVA (polyvinyl alcohol) which accounts for 5 wt% of the mass of the secondary ball grinding material into the secondary ball grinding material for granulation, controlling the D50 of the size of the granulated powder to be about 80 mu m, putting the granulated powder into a die with the diameter of 12.5mm, and pressing the granulated powder into a green body with the diameter of 12.5mm multiplied by 6mm under 200 MPa; and (3) sintering the green body in air at 1400 ℃ for 4 hours to obtain the complex-phase microwave dielectric ceramic material: 0.79MgTiO3-0.21(0.3CaTiO3–0.7CaZrO3)。
EXAMPLE five
The molecular formula of the microwave ceramic material provided by the embodiment of the application is as follows: a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Wherein A is1-yBO3Is Ca (Zn)1/3Nb2/3)O3The formula of the microwave ceramic material provided by the embodiment of the present application is as follows: b Mg2TiO4–c((1-x)CaTiO3–x Ca(Zn1/3Nb2/3)O3)-d Mg2SiO4. Namely pair CaTiO3The B site of the compound is replaced, and the normal temperature phase-shifting material is (1-x) CaTiO3–x Ca(Zn1/3Nb2/3)O3The negative temperature drift phase material is Mg2SiO4And Mg2TiO4。
In this embodiment, b may be 0.68, c may be 0.14, d may be 0.18, and x may be 0.2, so that in this embodiment, the molecular formula of the microwave ceramic material is 0.68Mg2TiO4-0.14(0.8CaTiO3–0.2Ca(Zn1/ 3Nb2/3)O3)-0.18Mg2SiO4Wherein the preparation molecular formula is 0.68Mg2TiO4-0.14(0.8CaTiO3–0.2Ca(Zn1/ 3Nb2/3)O3)-0.18Mg2SiO4The microwave ceramic material of (1) can be prepared by two methods in the first embodiment, in the embodiment of the present application, the method 2 in the first embodiment is specifically taken as an example to prepare a microwave ceramic material, and the specific preparation method is as follows:
according to 0.68Mg2TiO4-0.14(0.8CaTiO3–0.2Ca(Zn1/3Nb2/3)O3)-0.18Mg2SiO4Weighing basic magnesium carbonate (analytically pure), calcium carbonate (analytically pure), zinc oxide (analytically pure), tantalum oxide (analytically pure), silicon dioxide (analytically pure) and titanium oxide (analytically pure) as raw materials, mixing, putting the prepared mixture into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and carrying out primary ball milling for 8 hours, wherein the ratio of the added materials to the zirconium balls is 1: 5; and (4) taking out the slurry after ball milling, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain the primary ball grinding material. And pre-burning the primary ball grinding material for 6 hours at the temperature of 1200 ℃ to obtain a pre-burnt material. Putting the pre-sintered material into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding the material and the zirconium balls at a ratio of 1:5 to perform secondary ball milling for 6 hours; after ball milling, taking out the slurry, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain a secondPerforming secondary ball milling; adding PVA (polyvinyl alcohol) which accounts for 5 wt% of the mass of the secondary ball grinding material into the secondary ball grinding material for granulation, controlling the D50 of the size of the granulated powder to be about 80 mu m, putting the granulated powder into a die with the diameter of 12.5mm, and pressing the granulated powder into a green body with the diameter of 12.5mm multiplied by 6mm under 200 MPa; and (3) sintering the green body in air at 1400 ℃ for 4 hours to obtain the complex-phase microwave dielectric ceramic material: 0.68Mg2TiO4-0.14(0.8CaTiO3–0.2Ca(Zn1/3Nb2/3)O3)-0.18Mg2SiO4。
EXAMPLE six
The molecular formula of the microwave ceramic material provided by the embodiment of the application is as follows: a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Wherein A is1-yBO3Is La (Mg)1/2Ti1/2)O3The formula of the microwave ceramic material provided by the embodiment of the present invention is as follows: c ((1-x) CaTiO)3–x La(Mg1/2Ti1/2)O3)-d Mg2SiO4. Namely pair CaTiO3The A site (Ca) and the B site (Ti) are both substituted, and the positive temperature drift material is (1-x) CaTiO3–x La(Mg1/ 2Ti1/2)O3The negative temperature drift phase material is Mg2SiO4。
In this embodiment, c may be 0.29, d may be 0.71, and x may be 0.2, so that in this embodiment, the molecular formula of the microwave ceramic material is 0.29(0.8 CaTiO)3–0.2La(Mg1/2Ti1/2)O3)-0.71Mg2SiO4Wherein the preparation molecular formula is 0.29(0.8 CaTiO)3–0.2La(Mg1/2Ti1/2)O3)-0.71Mg2SiO4The microwave ceramic material of (1) can be prepared by the two methods described in the above first embodiment, in this application, the method 2 in the above first embodiment is specifically used as an example to prepare a microwave ceramic material, and the specific preparation method is as follows:
according to 0.29 (0.8)CaTiO3–0.2La(Mg1/2Ti1/2)O3)-0.71Mg2SiO4Weighing basic magnesium carbonate (analytically pure), calcium carbonate (analytically pure), lanthanum oxide (analytically pure), SiO2 (analytically pure) and titanium oxide (analytically pure) as raw materials, mixing, putting the prepared mixture into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, adding materials and the zirconium balls in a ratio of 1:5, and performing primary ball milling for 8 hours; and (4) taking out the slurry after ball milling, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain the primary ball grinding material. And pre-burning the primary ball grinding material for 6 hours at the temperature of 1200 ℃ to obtain a pre-burnt material. Putting the pre-sintered material into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding the material and the zirconium balls at a ratio of 1:5 to perform secondary ball milling for 6 hours; after ball milling, taking out the slurry, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain a secondary ball grinding material; adding PVA (polyvinyl alcohol) which accounts for 5 wt% of the mass of the secondary ball grinding material into the secondary ball grinding material for granulation, controlling the D50 of the size of the granulated powder to be about 80 mu m, putting the granulated powder into a die with the diameter of 12.5mm, and pressing the granulated powder into a green body with the diameter of 12.5mm multiplied by 6mm under 200 MPa; and (3) sintering the green body in air at a temperature of 1380 ℃ for 4 hours to obtain the final microwave dielectric ceramic material: 0.29(0.8 CaTiO)3–0.2La(Mg1/2Ti1/2)O3)-0.71Mg2SiO4。
In order to compare with the microwave ceramic materials prepared in the first to sixth examples, the examples of the present application further provide two comparative tests:
comparative experiment 1:
the molecular formula of the microwave ceramic material is aMgTiO3–c CaTiO3Where a is 0.95 and c is 0.05, according to 0.95MgTiO3–0.05CaTiO3Weighing basic magnesium carbonate (analytically pure), calcium carbonate (analytically pure) and titanium oxide (analytically pure) as raw materials, mixing the mixed materials in a nylon ball milling tank, using zirconium balls as milling balls and using deionized water as grinding ballsAdding a ball milling medium into the mixture, wherein the ratio of the materials to the zirconium balls is 1:5, and carrying out primary ball milling for 8 hours; after ball milling, taking out the slurry, drying the slurry for 4 hours at 120 ℃, sieving the slurry by a 40-mesh sieve to obtain a primary ball grinding material, and pre-sintering the primary ball grinding material for 6 hours at 1200 ℃ to obtain a pre-sintered material; putting the pre-sintered material into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding the material and the zirconium balls at a ratio of 1:5 to perform secondary ball milling for 6 hours; after ball milling, taking out the slurry, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain a secondary ball grinding material; adding PVA (polyvinyl alcohol) which accounts for 5 wt% of the mass of the secondary ball grinding material into the secondary ball grinding material for granulation, controlling the D50 of the size of the granulated powder to be about 80 mu m, putting the granulated powder into a die with the diameter of 12.5mm, and pressing the granulated powder into a green body with the diameter of 12.5mm multiplied by 6mm under 200 MPa; and (3) sintering the green body in the air at the temperature of 1350 ℃ for 4 hours to obtain the microwave dielectric ceramic material of the comparative test 1.
Comparative experiment 2:
the molecular formula of the microwave ceramic material is aMgTiO3–c CaTiO3Where a is 0.94 and c is 0.06, according to 0.94MgTiO3–0.06CaTiO3Weighing basic magnesium carbonate (analytically pure), calcium carbonate (analytically pure) and titanium oxide (analytically pure) as raw materials for mixing, putting the mixed material into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and carrying out primary ball milling for 8 hours, wherein the ratio of the added materials to the zirconium balls is 1: 5; after ball milling, taking out the slurry, drying the slurry for 4 hours at 120 ℃, sieving the slurry by a 40-mesh sieve to obtain a primary ball grinding material, and pre-sintering the primary ball grinding material for 6 hours at 1200 ℃ to obtain a pre-sintered material; putting the pre-sintered material into a nylon ball milling tank, taking zirconium balls as milling balls, taking deionized water as a ball milling medium, and adding the material and the zirconium balls at a ratio of 1:5 to perform secondary ball milling for 6 hours; after ball milling, taking out the slurry, drying the slurry for 4 hours at 120 ℃, and sieving the slurry by a 40-mesh sieve to obtain a secondary ball grinding material; adding PVA in an amount of 5 wt% of the secondary ball grinding material to the secondary ball grinding material for granulation, controlling the D50 of the granulated powder size to be about 80 mu m, and mixing the granulesPutting the granulated powder into a die with the diameter of 12.5mm and pressing the granulated powder into a green body with the diameter of 12.5mm multiplied by 6mm under 200 MPa; and (3) sintering the green body in the air at the temperature of 1350 ℃ for 4 hours to obtain the microwave dielectric ceramic material of the comparative test 2.
The microwave ceramic materials obtained in the above-described first, second, third, fourth, fifth, sixth, comparative tests 1 and 2 were tested.
Specifically, the dielectric constant and Qf value of the sample at high frequency were measured by a network analyzer (keysight 5222a) according to the Hakki-Coleman dielectric resonance method. The frequency drift is that the resonant frequency of a test sample is tested under the conditions of-40, 20, 0, 25, 40, 60, 80, 100 and 110 ℃, the maximum resonant frequency variation of 25 ℃ is taken within the range of-40 to 25 ℃, 25 to 110 ℃ and-40 to 110 ℃ on the basis of 25 ℃, and the maximum resonant frequency variation is divided by the resonant frequency of 25 ℃ to obtain the frequency drift delta f/f25℃A negative value indicates a shift of the resonant frequency to a low frequency at 25 ℃ and a positive value indicates a shift of the resonant frequency to a high frequency at 25 ℃.
The test results for each example are shown in table 1:
from table 1, it can be derived: compared with comparative test 1 and comparative test 2, in the first, second, third, fourth, fifth and sixth examples of the present application, the dielectric constant of the prepared microwave ceramic material is less than 22, the dielectric constant (i.e. less than or equal to 22) required by the microwave ceramic material is satisfied, the Qf value of the prepared microwave ceramic material is greater than 40THz, the high Qf value (i.e. more than 40THz) required by the microwave ceramic material is satisfied, and the delta f/f in the wide temperature region of-40 ℃ to 110 DEG C25℃All are negative values, so the resonance frequency shifts to low frequency relative to 25 ℃, and delta f/f in a wide temperature region of-40 ℃ to 110 DEG C25℃Less than or equal to 200ppm, therefore, the microwave ceramic material provided by the embodiment of the application meets the requirement that the microwave ceramic material is delta f/f in a wide temperature range of-40-110 DEG C25℃Less than 400 ppm.
The composite phase microwave ceramic material provided by the embodiment is prepared by subjecting CaTiO3A site and B site of or to CaTiO3Is doped and modified at the B site, so as to obtain the microwave ceramicThe material meets the dielectric constant (less than or equal to 22) expected for microwave dielectric ceramics and has low frequency drift (namely, the frequency drift in a wide temperature range<400ppm) and high Qf values (i.e.>40THz), so that the complex phase microwave ceramic material provided by the embodiment of the application is a microwave dielectric ceramic material with low resonant frequency temperature coefficient in a wide temperature zone, and the problem of the existing MgTiO is solved3-CaTiO3The composite ceramic has the problems of large vf and high frequency drift in a wide temperature range of-40 to 25 ℃.
TABLE 1
An embodiment of the present application further provides an electronic device, which at least includes: the microwave ceramic part is made of the complex phase microwave ceramic material in the embodiment, or the microwave ceramic part is made of the complex phase microwave ceramic material prepared by the manufacturing method of the complex phase microwave ceramic material in any embodiment.
The electronic device provided by the embodiment of the application can be a device made of ceramic materials, such as a resonator, a combiner, a dielectric antenna, a filter, an oscillator and the like.
The electronic device that this application embodiment provided adopts the aforesaid through microwave ceramic piece complex phase microwave ceramic material makes, make this electronic device have low frequency drift and low resonant frequency temperature coefficient in wide warm district like this, and because this complex phase microwave ceramic material has high Qf value, make electronic device realize miniaturization and low cost, solved current microwave ceramic material and can't satisfy the low resonant frequency temperature coefficient that microwave dielectric ceramic required, low frequency drift and high Qf value and lead to the electronic device performance that ceramic material made low and bulky scheduling problem.
In the description of the embodiments of the present application, it should be noted that unless otherwise explicitly stated or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, a fixed connection, an indirect connection via an intermediary, a connection between two elements, or an interaction between two elements. The specific meanings of the above terms in the embodiments of the present application can be understood by those of ordinary skill in the art according to specific situations.
The description and claims of the embodiments of the present application, and the terms "first," "second," "third," "fourth," and the like (if any), in the foregoing description are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the embodiments of the present application, and are not limited thereto; although the embodiments of the present application have been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Claims (4)
1. The complex-phase microwave ceramic material is characterized in that the molecular formula of a main component compound is as follows:
a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4
wherein the content of the first and second substances,
a is at least one of Ca, RE and Sr, wherein RE is a rare earth element and at least contains La;
the B is at least one of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr and Ga, and when the A is Ca or Sr, the B is one or more of Sn and Zr, and when the A is Ca or Sr, the B is Mg1/3Nb2/3,Zn1/3Nb2/3,Al1/2Nb1/2,Ga1/2Nb1/2When said a is RE, said B is one or more of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr;
c isMg1-m-n-qZnmConNiqM is more than or equal to 0 and less than or equal to 0.3, n is more than or equal to 0 and less than or equal to 0.3, and q is more than or equal to 0 and less than or equal to 0.3;
d is Ti1-t-wSntZrwT is more than or equal to 0 and less than or equal to 0.1, and w is more than or equal to 0 and less than or equal to 0.1;
e is SirGe1-rAnd r is more than or equal to 0.7 and less than or equal to 1;
a is more than or equal to 0 and less than or equal to 0.95, b is more than or equal to 0.95, c is more than or equal to 0.05 and less than or equal to 0.4, d is more than or equal to 0 and less than or equal to 0.8, a + b + c + d is 1, x is more than 0.05 and less than or equal to 0.7, and y is more than or equal to 0 and less than or equal to 0.35.
2. The preparation method of the complex-phase microwave ceramic material is characterized by comprising the following steps of:
according to a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4CO and DO in the component2、CaO、TiO2、ApOq、BsOw、MgO、EO2Weighing the following raw materials in a molar ratio: one of CO, C carbonate and C basic carbonate and DO2Calcium carbonate, TiO2、ApOq、BsOw、MgO、EO2；
Mixing the raw materials, performing ball milling, drying and sieving the ball-milled mixture, and pre-sintering at 900-1400 ℃ for 2-10 hours to obtain a pre-sintered material;
finely grinding and drying the pre-sintered material, mixing the pre-sintered material with a binder solution, and granulating, wherein the granulation size D50 is 40-100 um;
putting the granules obtained by granulation into a forming grinding tool for dry pressing and forming to obtain a green body;
sintering the green body at 1250-1500 ℃ for 1.5-6 h to obtain the complex-phase microwave dielectric ceramic material;
a is at least one of Ca, RE and Sr, wherein RE is a rare earth element and at least contains La;
the B is at least one of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr and GaWhen A is Ca or Sr, the B is one or more of Sn and Zr, and when A is Ca or Sr, the B is Mg1/3Nb2/3,Zn1/3Nb2/3,Al1/2Nb1/2,Ga1/2Nb1/2When said a is RE, said B is one or more of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr;
c is Mg1-m-n-qZnmConNiqM is more than or equal to 0 and less than or equal to 0.3, n is more than or equal to 0 and less than or equal to 0.3, and q is more than or equal to 0 and less than or equal to 0.3;
d is Ti1-t-wSntZrwT is more than or equal to 0 and less than or equal to 0.1, and w is more than or equal to 0 and less than or equal to 0.1;
e is SirGe1-rAnd r is more than or equal to 0.7 and less than or equal to 1;
a is more than or equal to 0 and less than or equal to 0.95, b is more than or equal to 0.95, c is more than or equal to 0.05 and less than or equal to 0.4, d is more than or equal to 0 and less than or equal to 0.8, a + b + c + d is 1, x is more than 0.05 and less than or equal to 0.7, and y is more than or equal to 0 and less than or equal to 0.35;
q, p, s and w are positive integers.
3. The preparation method of the complex-phase microwave ceramic material is characterized by comprising the following steps of:
according to a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Middle CO and DO2Weighing the following raw materials in a molar ratio: one of CO, C carbonate and C basic carbonate and DO2Mixing the raw materials, ball-milling, drying, sieving, and presintering at 900-1400 ℃ for 2-10 h to obtain CDO3And C2DO4；
According to a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Medium CaO, TiO2、ApOq、BsOwWeighing the following raw materials in a molar ratio: calcium carbonate, TiO2、ApOq、BsOwAnd mixing calcium carbonate and TiO2、ApOq、BsOwBall-milling, drying, sieving, and presintering at 900-1400 deg.C for 2-10 h to obtain (1-x) CaTiO3–x A1-yBO3；
According to a CDO3–b C2DO4–c((1-x)CaTiO3–x A1-yBO3)–d Mg2EO4Medium MgO, EO2Weighing raw materials in a molar ratio: one of MgO, magnesium carbonate and basic magnesium carbonate and EO2And mixing EO2And MgO or magnesium carbonate or basic magnesium carbonate are subjected to ball milling, drying and sieving, and then are presintered for 2-10 hours at the temperature of 900-1400 ℃ to prepare Mg2EO4；
A CDO3、b C2DO4、c((1-x)CaTiO3–x A1-yBO3) And d Mg2EO4Mixing, performing ball milling, drying, mixing with a binder solution, and granulating, wherein the granulation size D50 is 40-100 um;
putting the granules obtained by granulation into a forming grinding tool for dry pressing and forming to obtain a green body;
sintering the green body at 1250-1500 ℃ for 1.5-6 h to obtain the complex-phase microwave dielectric ceramic material;
a is at least one of Ca, RE and Sr, wherein RE is a rare earth element and at least contains La;
the B is at least one of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr and Ga, and when the A is Ca or Sr, the B is one or more of Sn and Zr, and when the A is Ca or Sr, the B is Mg1/3Nb2/3,Zn1/3Nb2/3,Al1/2Nb1/2,Ga1/2Nb1/2When said a is RE, said B is one or more of Ti, Sn, Al, Mg, Zn, Nb, Ta, Zr;
c is Mg1-m-n-qZnmConNiqM is more than or equal to 0 and less than or equal to 0.3, n is more than or equal to 0 and less than or equal to 0.3, and q is more than or equal to 0 and less than or equal to 0.3;
d is Ti1-t-wSntZrwT is more than or equal to 0 and less than or equal to 0.1, and w is more than or equal to 0 and less than or equal to 0.1;
e is SirGe1-rAnd r is more than or equal to 0.7 and less than or equal to 1;
a is more than or equal to 0 and less than or equal to 0.95, b is more than or equal to 0.95, c is more than or equal to 0.05 and less than or equal to 0.4, d is more than or equal to 0 and less than or equal to 0.8, a + b + c + d is 1, x is more than 0.05 and less than or equal to 0.7, and y is more than or equal to 0 and less than or equal to 0.35;
q, p, s and w are positive integers.
4. An electronic device, characterized by comprising at least: a microwave ceramic part, wherein the microwave ceramic part is made of the complex phase microwave ceramic material of the claim 1, or the microwave ceramic part is made of the complex phase microwave ceramic material prepared by the manufacturing method of the complex phase microwave ceramic material of the claims 2-3.
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