CN110818405A - Microwave dielectric ceramic, preparation method thereof and 5G base station - Google Patents
Microwave dielectric ceramic, preparation method thereof and 5G base station Download PDFInfo
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- CN110818405A CN110818405A CN201911063348.4A CN201911063348A CN110818405A CN 110818405 A CN110818405 A CN 110818405A CN 201911063348 A CN201911063348 A CN 201911063348A CN 110818405 A CN110818405 A CN 110818405A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 138
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 71
- 239000011575 calcium Substances 0.000 claims abstract description 52
- 239000011777 magnesium Substances 0.000 claims abstract description 52
- ZBRDCOZOFFMPNX-UHFFFAOYSA-N [Ti].[Mg].[Ca] Chemical compound [Ti].[Mg].[Ca] ZBRDCOZOFFMPNX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 36
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 230000014509 gene expression Effects 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 239000012700 ceramic precursor Substances 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 12
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- 229910010293 ceramic material Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 229910001960 metal nitrate Inorganic materials 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
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Abstract
The invention provides a microwave dielectric ceramic, a preparation method thereof and a 5G base station, wherein the microwave dielectric ceramic is MO-doped Mg0.964Ca0.336TiO3The expression mode of the chemical composition is as follows: mg (magnesium)0.964Ca0.336TiO3-xMO (i); wherein MO is La2/3O、Al2/3At least one of O, ZnO, CeO, SmO, MnO and CoO; mg (magnesium)0.964Ca0.336TiO3The molar ratio to MO was: mg (magnesium)0.964Ca0.336TiO3: MO is 1: x; x is 0.001 to 0.05. The microwave dielectric ceramic provided by the invention is Mg0.964Ca0.336TiO3On the basis of the composite material, MO is doped, and the MO and the magnesium-calcium titanium matrix ceramic are compounded, so that the electrical property and the reliability of the ceramic can be improved, and the sintering temperature of the ceramic can be effectively reduced.
Description
Technical Field
The invention belongs to the technical field of ceramics, and particularly relates to a microwave dielectric ceramic, a preparation method thereof and a 5G base station.
Background
The microwave dielectric ceramic is a novel functional electronic ceramic material which is developed in the last 30 years and is applied to microwave frequency band (mainly ultrahigh frequency (UHF) and ultra-high frequency (SHF)) circuits as a dielectric material and completes one or more functions, is widely used as components such as resonators, filters, dielectric substrates, dielectric waveguide loops and the like in modern communications such as mobile communication, satellite communication, military radars, global positioning systems, Bluetooth technology, wireless local area networks and the like, and is a key basic material of modern communication technology.
The base station filter mainly comprises a metal cavity filter, a metal combined ceramic cavity filter and a ceramic filter, which are respectively used for 3G, 4G and 5G. At present, the main current of the 5G base station filter (frequency bands of 2.6G and 3.5G) is the dielectric constant of 21, magnesium calcium titanium (Mg)0.964Ca0.336TiO3MCT) based materials; the requirements for the material, besides the necessary mechanical strength and chemical stability, also need to meet the following dielectric property requirements: (1) has extremely low dielectric loss at microwave resonance frequency, i.e. high quality internal number (Q), to ensure excellent frequency-selecting characteristics and reduce the insertion loss of the device at high frequency, generally requiring Q x f>60000; (2) near zero temperature coefficient of resonance frequency (tau)f) So as to ensure the high stability of the resonant frequency of the device (the requirement of the device is-40 ℃ to 105 ℃ frequency temperature drift +/-500 k) in the environment with temperature change.
MCT-based ceramic materials used by domestic 5G filter manufacturers are mostly prepared by a traditional solid-phase method, in order to ensure the electrical performance of a material system, the sintering temperature of the MCT-based ceramic prepared by the traditional solid-phase method is above 1400 ℃, so that the MCT-based ceramic has the problem of high and low temperature reliability, and the performance of a base station filter is greatly reduced within about two months. And the functional ceramics prepared by the traditional solid phase method has the defects of brittleness (cracks), poor uniformity, poor toughness and strength and the like. At present, no related report of MCT-based microwave dielectric ceramics with sintering temperature below 1400 ℃, high quality factor (Q x f > 70000) and good reliability is found.
Therefore, the development of the MCT-based microwave dielectric ceramic with the sintering temperature below 1400 ℃ and extremely high quality factor has remarkable practical significance.
Disclosure of Invention
The invention aims to provide a microwave dielectric ceramic, and aims to solve the technical problems of high sintering temperature, poor quality factor and poor reliability of the microwave dielectric ceramic in the prior art.
The invention also aims to provide a preparation method of the microwave dielectric ceramic.
Still another object of the present invention is to provide a 5G base station.
In order to solve the technical problems, the invention adopts the following technical scheme: the microwave dielectric ceramic is Mg-Ca-Ti-based nano ceramic which is MO-doped Mg0.964Ca0.336TiO3The expression mode of the chemical composition is as follows: mg (magnesium)0.964Ca0.336TiO3-xMO(Ⅰ)；
Wherein MO is La2/3O、Al2/3At least one of O, ZnO, CeO, SmO, MnO and CoO;
the Mg0.964Ca0.336TiO3The molar ratio to the MO is 1: x;
x is 0.001 to 0.05.
Further, MO is ZnO, and x is 0.01-0.05; or
The MO is La2O3And x is 0.001 to 0.03; or
The MO is Al2O3And x is 0.001 to 0.04; or
The MO is MnO, and x is 0.001-0.005.
Further, the particle size of the magnesium-calcium-titanium-based nano ceramic powder is 100-300 nm.
The invention also provides a preparation method of the microwave dielectric ceramic, which comprises the following steps:
s1, taking a magnesium source, a calcium source, a titanium source and a complexing agent with the purity of more than 99% as starting raw materials, dissolving the starting raw materials in deionized water to form a solution, adding an M source, and dissolving to form a mixed solution; wherein M in the M source is a metal ion, and M is selected from La3+、Al3+、Zn2+、Ce2+、Sm2+、Mn2+、Co2+At least one of (1);
s2, adjusting the pH value of the mixed solution obtained in the step S1 to be 5-8, and continuously mixing uniformly to form transparent sol;
s3, drying the transparent sol prepared in the step S2 until dry gel is formed;
s4, pre-burning the xerogel obtained in the step S3 to obtain precursor powder of the magnesium-calcium-titanium-based nano ceramic;
s5, adding a dispersing agent, a release agent and a binder into the magnesium-calcium-titanium-based nano ceramic precursor powder synthesized in the step S4, and granulating and pressing to obtain a formed blank;
s6, sintering the formed blank obtained in the step S5 to prepare the magnesium-calcium-titanium-based nano ceramic, wherein the magnesium-calcium-titanium-based nano ceramic is MO-doped Mg0.964Ca0.336TiO3The expression mode of the chemical composition is as follows: mg (magnesium)0.964Ca0.336TiO3-xMO(Ⅰ)；
The magnesium-calcium titanium-based nano ceramic comprises the following components in parts by mole: mg (magnesium)0.964Ca0.336TiO3：MO＝1：x；
Wherein MO is La2/3O、Al2/3At least one of O, ZnO, CeO, SmO, MnO and CoO;
x is 0.001 to 0.05.
Further, in step S1, the molar ratio of the molar content of the complexing agent to the total molar content of the metal ions in the M source is (1.5-1.8): 1.
Further, in step S2, the pH value of the mixed solution in step S1 is adjusted to 5-8 at the temperature of 60-80 ℃, and the mixed solution is continuously mixed to form transparent sol.
Further, in step S3, the temperature of the drying process is 150 to 180 ℃.
Further, in step S4, the pre-firing process parameters are: the pre-sintering temperature is 600-800 ℃, and the pre-sintering time is 1-2 hours; the particle size of precursor powder of the magnesium-calcium-titanium-based nano ceramic is 50-500 nm.
Further, in step S6, the sintering process parameters are: the sintering temperature is 1250-1350 ℃, and the sintering time is 3-6 hours.
The invention also provides a 5G base station, and the material of the 5G base station comprises the microwave dielectric ceramic.
The microwave dielectric ceramic and the preparation method thereof provided by the invention have the beneficial effects that:
the microwave dielectric ceramic provided by the invention is prepared from Mg0.964Ca0.336TiO3Is doped with MO, wherein MO is La2/3O、Al2/3At least one of O, ZnO, CeO, SmO, MnO and CoO, and the oxides and Mg0.964Ca0.336TiO3The matrix is compounded, and the lattice form of the material is changed by utilizing the steric hindrance effect of the elements, so that the electrical property of the ceramic is improved, the sintering densification can be promoted in the sintering process, and the sintering temperature is effectively reduced. The microwave dielectric ceramic formed by the method not only has high dielectric constant and quality factor, but also has low temperature coefficient of resonance frequency. Specifically, the dielectric constant epsilon of the microwave dielectric ceramicr20.56-20.78, extremely high quality factor Qxf value of 70000-90000 GHz and near-zero resonant frequency temperature coefficient taufThe power filter has the advantages that the power filter is-3 ppm/DEG C, the impact time of high and low temperature is 3 months, the performance decline tendency is avoided, and the reliability of the 5G base station filter can be effectively improved.
The preparation method of the microwave dielectric ceramic provided by the invention adopts a magnesium source, a calcium source and a titanium source as raw materials, obtains MCT transparent sol with high microscopic uniformity at atomic level or at least molecular level in a solution mode, and simultaneously adds an M source with the functions of a modifier and a sintering aid in the mixed solution in a solution mode, thereby preparing MCT-based nano ceramic powder with uniform chemical components and particle size distribution, not only sintering at the temperature below 1350 ℃ to prepare compact and high-performance MCT-based nano ceramic, but also effectively reducing the industrial energy consumption of the material system.
The preparation method of the microwave dielectric ceramic provided by the invention fills the technical blank of MCT-based nano ceramic for 5G base stations with the sintering temperature below 1400 ℃ and extremely high quality factors, has simple process and convenient operation, and is suitable for large-scale industrial application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a microwave dielectric ceramic, which is a magnesium-calcium-titanium-based nano ceramic, wherein the magnesium-calcium-titanium-based nano ceramic is MO-doped Mg0.964Ca0.336TiO3The expression mode of the chemical composition is as follows: mg (magnesium)0.964Ca0.336TiO3+xMO(Ⅰ)；
Wherein MO is La2/3O、Al2/3At least one of O, ZnO, CeO, SmO, MnO and CoO;
Mg0.964Ca0.336TiO3the molar ratio to MO was: mg (magnesium)0.964Ca0.336TiO3：MO＝1：x；
x is 0.001 to 0.05.
It should be noted that the microwave dielectric ceramic of the invention is magnesium calcium titanium-based nano ceramic, and the theoretical density is more than 96%. The nano ceramic is a ceramic material with a nano-scale phase in a microstructure, namely the grain size, the grain boundary width, the second phase distribution, the defect size and the like of the ceramic are all on the level of nano-scale, the number of refined grain boundaries is greatly increased, the strength, the toughness and the superplasticity of the material can be greatly improved, and the material has important influence on the performances of electricity, heat, optics, magnetism and the like. The nano ceramic has unique properties different from the traditional ceramic due to the volume percentage of the nano ceramic in the interface, high surface activity, small size effect and disorder of the interface, thereby developing a new field for the utilization of materials.
Note that, in Mg0.964Ca0.336TiO3Is doped with MO, wherein MO isLa2/3O、Al2/3At least one of O, ZnO, CeO, SmO, MnO and CoO, and the oxides and Mg0.964Ca0.336TiO3The matrix is compounded, the lattice form of the material is changed by utilizing the steric hindrance effect of the elements, so that the electrical property of the ceramic is improved, meanwhile, the sintering densification is promoted in the sintering process, the sintering temperature is effectively reduced, and the formed microwave dielectric ceramic has high dielectric constant and quality factor and low temperature coefficient of resonant frequency. Specifically, the dielectric constant epsilon of the microwave dielectric ceramicr20.56-20.78, extremely high quality factor Qxf value of 70000-90000 GHz and near-zero resonant frequency temperature coefficient taufThe power filter has the advantages that the power filter is-3 ppm/DEG C, the impact time of high and low temperature is 3 months, the performance decline tendency is avoided, and the reliability of the 5G base station filter can be effectively improved.
It should be noted that the molar ratio of the matrix ceramic to MO, i.e. the size of x, has a large influence on the electrical properties such as the dielectric constant, the quality factor, the temperature coefficient of resonant frequency, and the like of the MCT-based nano ceramic, if x is too small, the amount of doped MO is too small, which cannot effectively modify the matrix ceramic and effectively reduce the sintering temperature, and if x is too large, the amount of doped MO is too large, and after the amount of doped MO reaches a certain degree, the modifying effect and the sintering aid effect of MO are not increased along with the increase of MO content, so that the cost is increased only due to the too much doped MO. In the invention, x is selected from the range of 0.001-0.05, and MO doped in the range can play a role in modification and promote sintering densification in the sintering process, so that the electrical property of the ceramic can be improved, and the sintering temperature of the ceramic can be effectively reduced.
In some embodiments, MO is ZnO and x is 0.01-0.05.
In some embodiments, MO is La2O3And x is 0.001 to 0.03.
In some embodiments, MO is Al2O3And x is 0.001 to 0.04.
In some embodiments, MO is MnO and x is 0.001 to 0.005.
The invention also provides a preparation method of the microwave dielectric ceramic, which comprises the following steps:
s1, taking a magnesium source, a calcium source, a titanium source and a complexing agent with the purity of more than 99% as starting raw materials, dissolving the starting raw materials in deionized water to form a solution, adding an M source, and dissolving to form a mixed solution; wherein M in the M source is a metal ion, and M is selected from La3+、Al3+、Zn2+、Ce2+、Sm2+、Mn2+、Co2+At least one of (1);
s2, adjusting the pH value of the mixed solution obtained in the step S1 to be 5-8, and continuously mixing uniformly to form transparent sol;
s3, drying the transparent sol prepared in the step S2 until dry gel is formed;
s4, pre-burning the xerogel obtained in the step S3 to obtain precursor powder of the magnesium-calcium-titanium-based nano ceramic;
s5, adding a dispersing agent, a release agent and a binder into the magnesium-calcium-titanium-based nano ceramic precursor powder synthesized in the step S4, and granulating and pressing to obtain a formed blank;
s6, sintering the formed blank obtained in the step S5 to prepare the magnesium-calcium-titanium-based nano ceramic, wherein the magnesium-calcium-titanium-based nano ceramic is MO-doped Mg0.964Ca0.336TiO3The expression mode of the chemical composition is as follows: mg (magnesium)0.964Ca0.336TiO3-xMO(Ⅰ)；
The magnesium-calcium titanium-based nano ceramic comprises the following components in parts by mole: mg (magnesium)0.964Ca0.336TiO3：MO＝1：x；
Wherein MO is La2/3O、Al2/3At least one of O, ZnO, CeO, SmO, MnO and CoO;
x is 0.001 to 0.05.
The MCT-based microwave dielectric ceramic powder is obtained by adopting a Sol-Gel (Sol-Gel) method, and the method can obtain powder with uniform components and ultrafine particles, thereby greatly reducing the sintering temperature and the sintering time of the ceramic material and greatly improving the dielectric property of the ceramic material.
The preparation method of microwave dielectric ceramic provided by the invention adopts a magnesium source, a calcium source, a titanium source and citric acid as raw materials, MCT transparent sol with high microscopic uniformity on an atomic level or at least a molecular level is obtained in a solution mode, meanwhile, an M source containing metal ions is added into the mixed solution in a solution mode, so that MCT-based dielectric ceramic nano-powder with uniform chemical components and particle size distribution is prepared, the M source forms metal oxide after reaction, the metal oxide and matrix ceramic are co-sintered to form solid solution, lattice distortion is enabled to be activated, the sintering temperature is reduced, compact and high-performance MCT-based microwave dielectric nano-ceramic can be prepared by sintering at the temperature below 1350 ℃, and the industrial energy consumption of the material system can be effectively reduced.
In a further preferred embodiment of the present invention, in step S1, the molar ratio of the molar content of the complexing agent to the total molar amount of the metal ions in the M source is (1.5 to 1.8): 1.
The complexing agent of the present invention may be any one of alcohol, acetic acid, or citric acid, and in the embodiment of the present invention, citric acid is preferred, and a complex is formed by citric acid and metal ions such as magnesium, calcium, and titanium, and then a complex gel is formed through a sol-gel process, and nanoparticles with uniform particles are generated after low-temperature heat treatment, which is beneficial to sintering at a lower temperature to form a ceramic in a subsequent sintering process.
It should be noted that the addition amount of the complexing agent in the invention has a great influence on the whole complexing reaction, and if the addition amount of the complexing agent is small, the complexing reaction is incomplete, so that the complex gel formed in the sol-gel process is insufficient, and finally, nanoparticles with uniform particles cannot be obtained, which is not beneficial to subsequent sintering at a lower temperature; if the addition amount of the complexing agent is too large, part of the complexing agent still remains after the complexing reaction is completed, complex gel cannot be formed in the sol-gel process, and the prepared powder has poor activity, so that the sintering temperature is higher.
In a further preferred embodiment of the present invention, in step S2, the pH of the mixed solution of step S1 is adjusted to 5 to 8 with ammonia water at a temperature of 60 to 80 ℃, and the mixed solution is continuously kneaded to form a transparent sol.
It should be noted that ammonia water is used as a pH adjusting reagent, and can be completely volatilized in a gas form at the temperature, so that any new element cannot be generated in the subsequent reaction process to influence the reaction process. The pH value of the invention is important for the synthetic phase in the sol process, and in the pH value range, the synthetic MCT-based ceramic phase is stable and single, has no impurity phase interference, is easy to implement doping modification, and obtains the MCT transparent sol with high microcosmic uniformity.
In a further preferred embodiment of the present invention, in step S3, the drying temperature is 150 to 180 ℃.
As a further preferred aspect of the present invention, in step S4, the process parameters of the pre-firing are: the pre-sintering temperature is 600-800 ℃, and the pre-sintering time is 1-2 hours; the particle size of precursor powder of the magnesium-calcium titanium-based nano ceramic is 50-500 nm.
It should be noted that, as the pre-sintering temperature is increased continuously, the pre-sintering time is prolonged continuously, the crystal grains are gradually increased, the activity of the prepared precursor powder is poor, but the subsequent sintering temperature is too high due to too large crystal grains, and the electrical property and toughness of the ceramic material are poor. Under the condition of the pre-sintering process, the particle size of the obtained magnesium-calcium-titanium-based ceramic precursor powder is 50-500 nm, the particle size is below 1 mu m, the powder activity is good, the subsequent sintering temperature is facilitated, and the MCT-based nano ceramic with extremely high quality factor is obtained.
As a further preferred aspect of the present invention, in step S6, the sintering process parameters are: the sintering temperature is 1250-1350 ℃, and the sintering time is 3-6 hours.
It should be noted that the sintering process parameters have a good repairing effect on subsequent ceramic formation, materials at a few dead corners may not be completely reacted in the pre-sintering process, the uniformity of the size of crystal grains is effectively improved after sintering treatment, the material reaction tends to be more sufficient, however, too high temperature may cause the electrical property and toughness of the ceramic material to be poor, and too low temperature may cause incomplete sintering, and MCT-based nano-ceramic with extremely high quality factor and proper dielectric constant cannot be obtained. A large number of experiments show that the optimal sintering temperature and the optimal sintering time of the MCT-based nano ceramic are 1250-1350 ℃ and 3-6 hours respectively, and under the condition, the MCT-based nano ceramic has an extremely high quality factor, a proper dielectric constant and a near-zero resonant frequency temperature coefficient.
The invention also provides a 5G base station, and the material of the 5G base station comprises the microwave dielectric ceramic.
The preparation method of the microwave dielectric ceramic provided by the invention fills the technical blank of MCT-based microwave dielectric ceramic for 5G base stations with the sintering temperature below 1400 ℃ and extremely high quality factors, has simple process and convenient operation, and is suitable for large-scale industrial application.
In order to explain the technical solution of the present invention, the following detailed description is made with reference to specific examples.
Example 1
The present embodiment provides a microwave dielectric ceramic, whose chemical composition is expressed as follows: mg (magnesium)0.964Ca0.336TiO3-0.005MnO-0.05ZnO, wherein the microwave dielectric ceramic is MnO and ZnO doped MCT-based nano ceramic, and Mg0.964Ca0.336TiO3The mol ratio of MnO and ZnO is as follows: mg (magnesium)0.964Ca0.336TiO3：MnO：ZnO＝1:0.005:0.05。
The embodiment also provides a preparation method of the microwave dielectric ceramic, which comprises the following steps:
s1, taking magnesium nitrate, calcium nitrate, butyl titanate and citric acid with the purity of more than 99% as starting raw materials, dissolving the starting raw materials in deionized water, wherein the total molar ratio of the citric acid to the metal nitrate is 1.5:1 to form a solution, and then adding manganese nitrate and zinc nitrate according to the proportion to dissolve the solution to form a mixed solution;
s2, slowly adding ammonia water into the mixed solution obtained in the step S1 at 80 ℃ until the pH value is 5-8, and continuously stirring to form transparent sol;
s3, drying the transparent sol prepared in the step S2 in an oven at 180 ℃ until dry gel is formed;
s4, pre-sintering the xerogel obtained in the step S3, wherein the pre-sintering temperature is 650 ℃, and the pre-sintering time is 2 hours, so as to obtain precursor powder of the magnesium-calcium-titanium-based nano ceramic; wherein the particle size of precursor powder of the magnesium-calcium-titanium-based nano ceramic is 50-500 nm;
s5, adding a dispersing agent, a release agent and a binder into the magnesium-calcium-titanium-based nano ceramic precursor powder synthesized in the step S4, and granulating and press-forming;
s6, sintering the formed blank in the step S5 in a muffle furnace at the sintering temperature of 1320 ℃ for 4 hours to obtain the MCT-based nano ceramic.
Example 2
The present embodiment provides a microwave dielectric ceramic, whose chemical composition is expressed as follows: mg (magnesium)0.964Ca0.336TiO3-0.05ZnO-0.03La2O3-0.04Al2O3The microwave dielectric ceramic is ZnO or La2O3And Al2O3Doped MCT-based nanoceramics, Mg0.964Ca0.336TiO3With ZnO, La2O3、Al2O3The molar ratio of (A) to (B) is: mg (magnesium)0.964Ca0.336TiO3：ZnO：La2O3：Al2O3＝1:0.05:0.03:0.04。
The embodiment also provides a preparation method of the microwave dielectric ceramic, which comprises the following steps:
s1, taking magnesium nitrate, calcium nitrate, butyl titanate and citric acid with purity of more than 99% as starting raw materials, dissolving the starting raw materials in deionized water, wherein the total molar ratio of the citric acid to the metal nitrate is 1.5:1 to form a solution, then adding lanthanum nitrate, zinc nitrate and aluminum nitrate according to the proportion, and dissolving to form a mixed solution;
s2, slowly adding ammonia water into the mixed solution obtained in the step S1 at 80 ℃ until the pH value is 5-8, and continuously stirring to form transparent sol;
s3, drying the transparent sol prepared in the step S2 in an oven at 180 ℃ until dry gel is formed;
s4, pre-sintering the xerogel obtained in the step S3 at the pre-sintering temperature of 750 ℃ for 2 hours to obtain precursor powder of the magnesium-calcium-titanium-based nano ceramic; wherein the particle size of precursor powder of the magnesium-calcium-titanium-based nano ceramic is 100-300 nm;
s5, adding a dispersing agent, a release agent and a binder into the magnesium-calcium-titanium-based nano ceramic precursor powder synthesized in the step S4, and granulating and press-forming;
s6, sintering the formed blank in the step S5 in a muffle furnace at 1280 ℃ for 4 hours to obtain the MCT-based nano ceramic.
Example 3
The present embodiment provides a microwave dielectric ceramic, whose chemical composition is expressed as follows: mg (magnesium)0.964Ca0.336TiO30.01ZnO-0.001CeO-0.05CoO, the microwave dielectric ceramic is MCT-based nano ceramic doped with ZnO, CeO and CoO, and Mg0.964Ca0.336TiO3With ZnO, CeO, CoO3The molar ratio of (A) to (B) is: mg (magnesium)0.964Ca0.336TiO3：ZnO：CeO：CoO3＝1:0.01:0.001:0.05。
The embodiment also provides a preparation method of the microwave dielectric ceramic, which comprises the following steps:
s1, taking magnesium nitrate, calcium nitrate, butyl titanate and citric acid with purity of more than 99% as starting raw materials, dissolving the starting raw materials in deionized water, wherein the total molar ratio of the citric acid to the metal nitrate is 1.8:1 to form a solution, and then adding zinc nitrate, cerium nitrate and cobalt nitrate according to the proportion to dissolve the solution to form a mixed solution;
s2, slowly adding ammonia water into the mixed solution obtained in the step S1 at 70 ℃ until the pH value is 5-8, and continuously stirring to form transparent sol;
s3, drying the transparent sol prepared in the step S2 in a drying oven at 160 ℃ until dry gel is formed;
s4, pre-sintering the xerogel obtained in the step S3 at the pre-sintering temperature of 600 ℃ for 1.5 hours to obtain precursor powder of the magnesium-calcium-titanium-based nano ceramic; wherein the particle size of precursor powder of the magnesium-calcium-titanium-based nano ceramic is 100-400 nm;
s5, adding a dispersing agent, a release agent and a binder into the magnesium-calcium-titanium-based nano ceramic precursor powder synthesized in the step S4, and granulating and press-forming;
s6, sintering the formed blank in the step S5 in a muffle furnace at 1250 ℃ for 6 hours to obtain the MCT-based nano ceramic.
Example 4
The present embodiment provides a microwave dielectric ceramic, whose chemical composition is expressed as follows: mg (magnesium)0.964Ca0.336TiO3-0.001MnO-0.02SmO-0.008Al2O3The microwave dielectric ceramics are MnO, SmO and Al2O3Doped MCT-based nanoceramics, Mg0.964Ca0.336TiO3With MnO, SmO, Al2O3The molar ratio of (A) to (B) is: mg (magnesium)0.964Ca0.336TiO3：MnO：SmO：Al2O3＝1:0.001:0.02:0.008。
The embodiment also provides a preparation method of the microwave dielectric ceramic, which comprises the following steps:
s1, taking magnesium nitrate, calcium nitrate, butyl titanate and citric acid with the purity of more than 99% as starting raw materials, dissolving the starting raw materials in deionized water, wherein the total molar ratio of the citric acid to the metal nitrate is 1.6:1 to form a solution, then adding manganese nitrate, samarium nitrate and aluminum nitrate according to the proportion, and dissolving to form a mixed solution;
s2, slowly adding ammonia water into the mixed solution obtained in the step S1 at 60 ℃ until the pH value is 5-8, and continuously stirring to form transparent sol;
s3, drying the transparent sol prepared in the step S2 in a drying oven at 160 ℃ until dry gel is formed;
s4, pre-sintering the xerogel obtained in the step S3 at 800 ℃ for 1 hour to obtain precursor powder of the magnesium-calcium-titanium-based nano ceramic; wherein the particle size of precursor powder of the magnesium-calcium-titanium-based nano ceramic is 50-400 nm;
s5, adding a dispersing agent, a release agent and a binder into the magnesium-calcium-titanium-based nano ceramic precursor powder synthesized in the step S4, and granulating and press-forming;
s6, sintering the formed blank in the step S5 in a muffle furnace at 1350 ℃ for 3 hours to obtain the magnesium-calcium-titanium-based nano ceramic.
Comparative example 1
The comparative example provides a microwave dielectric ceramic whose chemical composition is expressed in the following manner: mg (magnesium)0.964Ca0.336TiO3-0.005CuO-0.05MgO, the microwave dielectric ceramic is CuO, MgO-doped MCT-based nano ceramic, Mg0.964Ca0.336TiO3The molar ratio of CuO to MgO is as follows: mg (magnesium)0.964Ca0.336TiO3：CuO：MgO＝1:0.005:0.05。
The comparative example also provides a preparation method of the microwave dielectric ceramic, which refers to the preparation method of the example 1.
Comparative example 2
This comparative example provides a microwave dielectric ceramic whose chemical composition is expressed in substantially the same manner as in example 1.
The comparative example also provides a preparation method of the microwave dielectric ceramic, and is different from the embodiment 1 in that the comparative example adopts a traditional solid phase method to prepare the microwave dielectric ceramic.
The microwave dielectric ceramic samples prepared in the examples 1 to 4 and the comparative examples 1 to 2 are subjected to performance detection, including quality factor (Qxf) and relative dielectric constant epsilonrAnd a resonant frequency temperature coefficient tau at a high temperature of 100 DEG CfThe specific test results are shown in Table 1.
TABLE 1
As can be seen from the above table, the MCT-based nano-ceramic samples prepared in the embodiments 1-4 of the invention have extremely high quality factor (Qxf) values and appropriate relative dielectric constants epsilonrAnd near zero resonant frequency temperatureCoefficient of degree τf(ii) a The MCT-based nano ceramic samples prepared in the comparative examples 1-2 have quality factor (Qxf) values lower than 60000GHz, relative dielectric constants smaller than those of the samples prepared in the examples 1-4 of the invention, and have higher temperature coefficients of resonance frequencies. The MCT-based nano ceramic provided by the invention is applied to Mg0.964Ca0.336TiO3Is doped with MO, wherein M is selected from at least one of 2/3La, 2/3Al, Zn, Ce, Sm, Mn and Co, and the elements and Mg0.964Ca0.336TiO3The substrate is compounded, so that the ceramic material can be densely sintered at 1350 ℃, and has good reliability.
Performance testing
Respectively carrying out high and low temperature storage tests and temperature impact tests on the microwave dielectric ceramic samples prepared in the examples 1-2 and the comparative examples 1-2, and respectively detecting the quality factor (Qxf) value and the relative dielectric constant epsilon of the samples after the testsrAnd a resonant frequency temperature coefficient tau at a high temperature of 100 DEG CfThe specific test results are shown in Table 2.
The high-low temperature storage test method comprises the following steps: the temperature is 100 ℃, the temperature is-40 ℃, the storage is 24 hours, the recovery is 2 hours, and 5 continuous cycles are carried out.
Temperature impact test method: the samples were subjected to 200 cycles with one cycle at a temperature between-40 ℃ and 100 ℃ over 2 minutes.
TABLE 2
As can be seen from the above table, the MCT-based nano-ceramics prepared in the embodiments 1-2 of the invention have the quality factor (Qxf) value and the relative dielectric constant epsilon after high and low temperature storage tests and temperature impact testsrAnd a resonant frequency temperature coefficient tau at a high temperature of 100 DEG CfThe electrical property is almost unchanged; in comparative examples 1-2, the sample quality factor value and the relative dielectric constant are large after high and low temperature storage test and temperature impact testThe amplitude is reduced, the temperature coefficient of the resonant frequency is obviously increased, and the MCT-based nano ceramic prepared by the comparative examples 1-2 is poor in reliability.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts of the present invention. It should be noted that there are no specific structures but a few objective structures due to the limited character expressions, and that those skilled in the art may make various improvements, decorations or changes without departing from the principle of the invention or may combine the above technical features in a suitable manner; such modifications, variations, combinations, or adaptations of the invention using its spirit and scope, as defined by the claims, may be directed to other uses and embodiments.
Claims (10)
1. The microwave dielectric ceramic is characterized in that the microwave dielectric ceramic is magnesium calcium titanium-based nano ceramic which is MO doped Mg0.964Ca0.336TiO3The expression mode of the chemical composition is as follows: mg (magnesium)0.964Ca0.336TiO3-xMO(Ⅰ)；
Wherein MO is La2/3O、Al2/3At least one of O, ZnO, CeO, SmO, MnO and CoO;
the Mg0.964Ca0.336TiO3The molar ratio to the MO is 1: x;
x is 0.001 to 0.05.
2. The microwave dielectric ceramic of claim 1, wherein MO is ZnO, and x is 0.01 to 0.05; or
The MO is La2O3And x is 0.001 to 0.03; or
The MO is Al2O3And x is 0.001 to 0.04; or
The MO is MnO, and x is 0.001-0.005.
3. The microwave dielectric ceramic of claim 1 or 2, wherein the particle size of the magnesium calcium titanium-based nano ceramic powder is 100-300 nm.
4. A method for preparing a microwave dielectric ceramic as claimed in any one of claims 1 to 3, comprising the steps of:
s1, taking a magnesium source, a calcium source, a titanium source and a complexing agent with the purity of more than 99% as starting raw materials, dissolving the starting raw materials in deionized water to form a solution, adding an M source, and dissolving to form a mixed solution; wherein M in the M source is a metal ion, and M is selected from La3+、Al3+、Zn2+、Ce2+、Sm2+、Mn2+、Co2+At least one of (1);
s2, adjusting the pH value of the mixed solution obtained in the step S1 to be 5-8, and continuously mixing uniformly to form transparent sol;
s3, drying the transparent sol prepared in the step S2 until dry gel is formed;
s4, pre-burning the xerogel obtained in the step S3 to obtain precursor powder of the magnesium-calcium-titanium-based nano ceramic;
s5, adding a dispersing agent, a release agent and a binder into the magnesium-calcium-titanium-based nano ceramic precursor powder synthesized in the step S4, and granulating and pressing to obtain a formed blank;
s6, sintering the formed blank obtained in the step S5 to prepare the magnesium-calcium-titanium-based nano ceramic, wherein the magnesium-calcium-titanium-based nano ceramic is MO-doped Mg0.964Ca0.336TiO3The expression mode of the chemical composition is as follows: mg (magnesium)0.964Ca0.336TiO3-xMO(Ⅰ)；
The magnesium-calcium titanium-based nano ceramic comprises the following components in parts by mole: mg (magnesium)0.964Ca0.336TiO3：MO＝1：x；
Wherein MO is La2/3O、Al2/3At least one of O, ZnO, CeO, SmO, MnO and CoO;
x is 0.001 to 0.05.
5. A preparation method of a microwave dielectric ceramic as claimed in claim 4, wherein in step S1, the molar ratio of the molar content of the complexing agent to the total molar content of the metal ions in the M source is (1.5-1.8): 1.
6. The method for preparing microwave dielectric ceramic according to claim 4, wherein in step S2, the pH of the mixed solution of step S1 is adjusted to 5-8 at a temperature of 60-80 ℃, and the mixed solution is continuously mixed to form a transparent sol.
7. The method for preparing microwave dielectric ceramic according to claim 4, wherein in step S3, the temperature of the drying treatment is 150-180 ℃.
8. A method for preparing microwave dielectric ceramic according to claim 4, wherein in step S4, the pre-sintering process parameters are: the pre-sintering temperature is 600-800 ℃, and the pre-sintering time is 1-2 hours; the particle size of precursor powder of the magnesium-calcium-titanium-based nano ceramic is 50-500 nm.
9. The method for preparing microwave dielectric ceramic according to claim 4, wherein in step S6, the sintering process parameters are: the sintering temperature is 1250-1350 ℃, and the sintering time is 3-6 hours.
10. A 5G base station, wherein the material of the 5G base station comprises the microwave dielectric ceramic of any one of claims 1 to 3.
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| CN111233462A (en) * | 2020-03-21 | 2020-06-05 | 东莞市钧鹏电子科技有限公司 | Medium microwave dielectric ceramic powder and preparation method thereof |
| CN111548148A (en) * | 2020-06-05 | 2020-08-18 | 陕西华星电子开发有限公司 | Microwave dielectric porcelain, preparation method and application |
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| CN114249347A (en) * | 2021-12-22 | 2022-03-29 | 元颉新材料科技(浙江)有限公司 | A kind of pure crystal phase nanometer size magnesium titanate ceramic powder and preparation method thereof |
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| CN111233462A (en) * | 2020-03-21 | 2020-06-05 | 东莞市钧鹏电子科技有限公司 | Medium microwave dielectric ceramic powder and preparation method thereof |
| CN111548148A (en) * | 2020-06-05 | 2020-08-18 | 陕西华星电子开发有限公司 | Microwave dielectric porcelain, preparation method and application |
| CN111848153A (en) * | 2020-08-06 | 2020-10-30 | 深圳市兆普莱科技有限公司 | Microwave dielectric ceramic, preparation method of microwave dielectric ceramic and communication device |
| CN114249347A (en) * | 2021-12-22 | 2022-03-29 | 元颉新材料科技(浙江)有限公司 | A kind of pure crystal phase nanometer size magnesium titanate ceramic powder and preparation method thereof |
| CN114195510A (en) * | 2021-12-28 | 2022-03-18 | 元颉新材料科技(浙江)有限公司 | A kind of pure crystal phase high quality factor nanometer size magnesium calcium titanate ceramic powder and preparation method thereof |
| CN114195510B (en) * | 2021-12-28 | 2024-04-23 | 元颉新材料科技(浙江)有限公司 | Pure crystal phase high-quality factor nano-sized magnesium calcium titanate ceramic powder and preparation method thereof |
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