CN113105230A - Microwave dielectric ceramic material for 5G base station and preparation method thereof - Google Patents
Microwave dielectric ceramic material for 5G base station and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 75
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000001035 drying Methods 0.000 claims abstract description 44
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 238000005469 granulation Methods 0.000 claims abstract description 20
- 230000003179 granulation Effects 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims description 202
- 238000002156 mixing Methods 0.000 claims description 79
- 239000002904 solvent Substances 0.000 claims description 72
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 56
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 44
- 239000002994 raw material Substances 0.000 claims description 44
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 42
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 41
- 238000007873 sieving Methods 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000011656 manganese carbonate Substances 0.000 claims description 23
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 23
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 22
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 22
- 239000001095 magnesium carbonate Substances 0.000 claims description 22
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 22
- 229940093474 manganese carbonate Drugs 0.000 claims description 22
- 235000006748 manganese carbonate Nutrition 0.000 claims description 22
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 22
- 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 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims description 22
- 239000004408 titanium dioxide Substances 0.000 claims description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000008187 granular material Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- 238000003825 pressing Methods 0.000 claims description 19
- 239000011575 calcium Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000035939 shock Effects 0.000 abstract description 14
- 239000000919 ceramic Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract 1
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009439 industrial construction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
The invention discloses a microwave dielectric ceramic material for a 5G base station and a preparation method thereof, wherein the ceramic material has a general formula: ca1‑xLaxTi1‑yAlyO3+a wt％Mg2Al4Si5O18+b wt％Nb2O5+c wt％ZrO2+ d wt% MnO, where x and y are molar content ratio, x is 0.2-0.4, and y is 0.2-0.4; a. b, c, d are in Ca1‑xLaxTi1‑yAlyO3A is more than or equal to 0.01 and less than or equal to 7B is more than or equal to 0.001 and less than or equal to 2, c is more than or equal to 0.001 and less than or equal to 5, and d is more than or equal to 0.001 and less than or equal to 0.5. The preparation method comprises the steps of material proportioning, ball milling, drying, pre-sintering, secondary ball milling, granulation, molding and sintering. The microwave dielectric ceramic material provided by the invention has excellent performance, particularly the thermal shock resistance is greatly improved, the thermal shock resistance temperature difference reaches more than 100 ℃, and the relative dielectric constant epsilon of the microwave dielectric ceramic materialrIs adjustable between 40 and 50, the Qxf value reaches above 40000, and the temperature coefficient tau of the resonant frequency isfCan be adjusted between-10 ppm/DEG C to +10 ppm/DEG C. The preparation method is simple in preparation process, stable in performance and high in reliability, and meets the actual use requirements of the microwave medium for the 5G base station.
Description
Technical Field
The invention belongs to the technical field of electronic information functional materials and devices, and particularly relates to a microwave dielectric ceramic material for a 5G base station and a preparation method thereof.
Background
In the 5G era, the human social information interaction mode is further upgraded, the service application types supported by the mobile communication network are richer and more diversified, various applications with high capacity and high rate are concurrent, and higher requirements are provided for the capacity, the rate and the service capability of the mobile network. Miniaturized equipment such as a micro base station, an active intelligent antenna and the like, which has high integration level, strong data carrying capacity and flexible and intelligent layout, becomes an important hardware guarantee for smooth operation of a 5G network and smooth application of the Internet of things and cloud technology. The radio frequency filter is used as a main core device of a micro base station and an active antenna system, and the development of integration and miniaturization is going to be carried out in the 5G era. The material and the preparation technology for seeking ideal key indexes such as dielectric constant, frequency temperature coefficient, thermal expansion coefficient and the like are key problems to be solved in the technical field of 5G radio frequency antennas, and have important strategic significance for high-quality comprehensive construction and development of 5G mobile communication infrastructures. In China, the active research and development of the novel high-performance microwave dielectric ceramic with the independent intellectual property rights has very important strategic significance for national defense and industrial construction.
In order to cope with the development direction of miniaturization, light weight and integration of the 5G base station, the filter is used as an indispensable core component of the base station, and inevitably faces the development trend of miniaturization and light weight. Meanwhile, the large-scale antenna array technology (Massive MIMO) increases the number of antenna channels from 2/4/8 in the 4G period to 64/128/256, so the requirement for the filter will increase greatly. The ceramic microwave medium has obvious advantages in small size, light weight and low cost due to high Q value, low loss and excellent temperature stability, and becomes the mainstream of the 5G base station filter.
CaTiO3-NdAlO3The system consists of two CaTiO with opposite frequency temperature coefficients3(τf803 ppm/° c) and NdAlO)3(τf-33ppm/° c), has excellent microwave dielectric properties: epsilonr＝45,Q×f＝45000GHz,τf0 to 6 ppm/DEG C. But Nd is one of the raw materials used in the system2O3Is expensive (more than 500 yuan/kg), resulting in CaTiO3-NdAlO3The cost of the system is always high, and the wide-range use of the system in the civil field is limited. Furthermore, in practical base station applications, the peak temperature may even beThe temperature of the microwave medium can reach 110-120 ℃, and in some high-latitude areas, the environmental temperature can be lower than-30 ℃, so that the microwave medium can repeatedly undergo a temperature rise-temperature reduction process, and due to the brittleness of the ceramic, the rapid temperature rise and drop resistance of the ceramic is poor, namely, the thermal shock resistance is poor, the device is cracked, failure is caused, and even the dielectric ceramic is collapsed when the device is serious, so that the device is destroyed. At present, the microwave dielectric ceramic material is required to have high quality factor and stable frequency temperature characteristic, and the reliability of the material and devices thereof under the condition of thermal shock is neglected. Therefore, it is urgently needed to develop a microwave dielectric ceramic material which has simple process and low raw material cost, and simultaneously satisfies high microwave dielectric property and high thermal shock resistance, so that the microwave dielectric ceramic material is applied to the construction of a 5G base station.
Disclosure of Invention
The invention aims to solve the defects in the prior art at least to a certain extent, and provides a microwave dielectric ceramic material for a 5G base station and a preparation method thereof.
In order to achieve the purpose, the invention provides a microwave dielectric ceramic material for a 5G base station, which has the following composition general formula: ca1-xLaxTi1-yAlyO3+a wt％Mg2Al4Si5O18+b wt％Nb2O5+c wt％ZrO2+ d wt% MnO, where x and y are molar content ratio, x is 0.2-0.4, and y is 0.2-0.4; a, b, c, d are in Ca1-xLaxTi1-yAlyO3The value ranges of the mass percentage contents are respectively as follows: a is more than or equal to 0.01 and less than or equal to 7, b is more than or equal to 0.001 and less than or equal to 2, c is more than or equal to 0.001 and less than or equal to 5, and d is more than or equal to 0.001 and less than or equal to 0.5.
Preferably, the value ranges of a, b, c and d are respectively as follows: a is more than or equal to 1 and less than or equal to 5.5, b is more than or equal to 0.1 and less than or equal to 1, c is more than or equal to 0.5 and less than or equal to 4, and d is more than or equal to 0.01 and less than or equal to 0.05.
The invention also provides a preparation method of the microwave dielectric ceramic material for the 5G base station, which comprises the following steps:
s1: calcium carbonate, lanthanum oxide and lanthanum oxideTitanium oxide and aluminum oxide as raw materials, according to the general formula Ca1-xLaxTi1-yAlyO3The molar content ratio of x is more than or equal to 0.2 and less than or equal to 0.4, and y is more than or equal to 0.2 and less than or equal to 0.4, and after grinding and mixing, drying to obtain dry powder;
s2: placing the dried powder obtained in the step S1 in a crucible for presintering to obtain presintering powder;
s3: basic magnesium carbonate, aluminum oxide and silicon dioxide are used as raw materials, and the formula is Mg2Al4Si5O18The components are mixed according to the molar content ratio, and after grinding and mixing, the dry powder is obtained after drying;
s4: placing the dried powder obtained in the step S3 in a crucible for presintering to obtain presintering powder;
s5: mixing and grinding the pre-sintered powder obtained in the step S2, the pre-sintered powder obtained in the step S4, zirconium dioxide, niobium pentaoxide and manganese carbonate according to the general formula of the ceramic material, and drying to obtain dry powder;
s6: mixing the dry powder obtained in the step S5 with a polyvinyl alcohol aqueous solution, granulating, and putting the granules into a forming die for dry pressing and forming to obtain a green body;
s7: and (5) placing the green body obtained in the step S6 on a setter plate to be sintered to obtain the final microwave dielectric ceramic material.
Preferably, the concentrations of the raw materials adopted are as follows: 99.5% of calcium carbonate, 99.9% of lanthanum oxide, 99.5% of titanium dioxide, 99.5% of aluminum oxide, 99.5% of zirconium dioxide, 99.9% of niobium pentoxide, 99% of basic magnesium carbonate, 99.5% of silicon dioxide and 99.5% of manganese carbonate.
Preferably, the mixture obtained by blending in step S1 and the mixture obtained by blending in step S3 are prepared by using zirconia balls as ball milling media and deionized water as a solvent, respectively, according to the following formula: ball milling media: solvent 1: 5: grinding for 4-8 hours according to the weight ratio of 1-3, drying and sieving by a sieve of 40-120 meshes to obtain dry powder.
Preferably, in the step S2, the dried powder obtained in the step S1 is placed in a crucible, and presintering and heat preservation are performed at 1100 to 1300 ℃ for 2 to 5 hours to obtain presintering powder; and step S4, pre-sintering the dried powder obtained in step S3 at 1200-1400 ℃ and keeping the temperature for 2-5 hours to obtain pre-sintered powder.
Preferably, the mixture obtained by blending in the step S5 is ball-milled for 2-6 hours, dried and sieved by a 40-120 mesh sieve to obtain dry powder.
Preferably, the granulation size in step S6 is 100 to 200 mesh.
Preferably, the green body in the step S7 is sintered for 2-6 hours at 1350-1550 ℃ to obtain the final microwave dielectric ceramic material.
Compared with the prior art, the invention has the following characteristics:
1. the thermal shock resistant temperature difference of the related system microwave ceramic material prepared by the prior art is below 70 ℃; in contrast, the thermal shock temperature difference of the microwave dielectric ceramic material provided by the invention can reach more than 100 ℃, is increased by 42.9%, and simultaneously still maintains excellent microwave dielectric property, the relative dielectric constant is 40-50, the Qxf value reaches more than 40000, and the resonant frequency temperature coefficient tau isfThe microwave dielectric ceramic material provided by the invention realizes great improvement on thermal shock resistance between-10 ppm/DEG C and +10 ppm/DEG C.
2. The microwave dielectric ceramic material does not contain volatile toxic metals such as Pb, Cd, Bi and the like, can be widely applied to microwave devices such as dielectric resonators, filters, oscillators and the like in satellite communication, is green, environment-friendly and pollution-free, and meets the strict standard requirements of the latest RHOS (instruction for limiting the use of certain harmful substances in electrical and electronic equipment) and the recycling management regulations (WEEE) in the European Union.
3. The raw materials are sufficient in China, the price is low, and the cost reduction of the high-performance microwave dielectric ceramic is possible.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The embodiment of the invention provides a dielectric waveguide filter ceramic material for a 5G base station, which has the following general formula: ca1- xLaxTi1-yAlyO3+a wt％Mg2Al4Si5O18+b wt％Nb2O5+c wt％ZrO2+ d wt% MnO, where x and y are molar content ratio, x is 0.2-0.4, and y is 0.2-0.4; a, b, c, d are in Ca1-xLaxTi1-yAlyO3The value ranges of the mass percentage contents are respectively as follows: a is more than or equal to 0.01 and less than or equal to 7, b is more than or equal to 0.001 and less than or equal to 2, c is more than or equal to 0.001 and less than or equal to 5, and d is more than or equal to 0.001 and less than or equal to 0.5; preferably, a is more than or equal to 1 and less than or equal to 5.5, b is more than or equal to 0.1 and less than or equal to 1, c is more than or equal to 0.5 and less than or equal to 4, and d is more than or equal to 0.01 and less than or equal to 0.05.
The preparation method of the dielectric waveguide filter ceramic material for the 5G base station comprises the following steps:
s1, calcium carbonate, lanthanum oxide, titanium dioxide and aluminum oxide are used as raw materials according to Ca1-xLaxTi1-yAlyO3The molar content ratio of (A) is more than or equal to 0.2 and less than or equal to 0.4, y is more than or equal to 0.2 and less than or equal to 0.4, the obtained mixture takes zirconia balls as a ball milling medium, deionized water as a solvent, and the weight ratio of the mixture: ball milling medium: solvent 1: 5: 1-3, grinding for 4-8 hours, drying, and sieving with a 40-120 mesh sieve to obtain dry powder;
s2: placing the dried powder obtained in the step S1 in a crucible, presintering at 1100-1300 ℃ and preserving heat for 2-5 hours to obtain presintering powder;
s3: basic magnesium carbonate, aluminum oxide and silicon dioxide are taken as raw materials according to Mg2Al4Si5O18The mixture is prepared by taking zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the molar content ratio of the mixture: ball milling medium: solvent 1: 5: 1 to 3 by weightGrinding for 4-8 hours, drying and sieving with a 40-120 mesh sieve to obtain dry powder;
s4: placing the dried powder obtained in the step S3 in a crucible, presintering at 1200-1400 ℃ and preserving heat for 2-5 hours to obtain presintering powder;
s5: mixing the pre-sintered powder obtained in the step S2 with the pre-sintered powder obtained in the step S4, and the zirconium dioxide, the niobium pentaoxide and the manganese carbonate according to the general formula of the ceramic material, ball-milling for 2-6 hours, drying, and sieving with a 40-120-mesh sieve to obtain dried powder;
s6: mixing the dry powder obtained in the step S5 with a polyvinyl alcohol aqueous solution, granulating, wherein the granulation size is 100-200 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body;
s7: and (5) placing the green body obtained in the step (S6) on a sintering bearing plate, and sintering at 1350-1550 ℃ for 2-6 hours to obtain the final microwave dielectric ceramic material.
Wherein the adopted raw materials have the following concentrations: 99.5% of calcium carbonate, 99.9% of lanthanum oxide, 99.5% of titanium dioxide, 99.5% of aluminum oxide, 99.5% of zirconium dioxide, 99.9% of niobium pentoxide, 99% of basic magnesium carbonate, 99.5% of silicon dioxide and 99.5% of manganese carbonate.
The invention is further illustrated by the following specific examples, Table 1 shows the general formula of Ca1- xLaxTi1-yAlyO3+a wt％Mg2Al4Si5O18+b wt％Nb2O5+c wt％ZrO2+d wt％MnCO3The microwave dielectric ceramic material is characterized in that x and y are molar content ratios, x is more than or equal to 0.2 and less than or equal to 0.4, and y is more than or equal to 0.2 and less than or equal to 0.4; a, b, c, d are in Ca1-xLaxTi1- yAlyO3Based on the mass percentage content, a is more than or equal to 1 and less than or equal to 5.5, b is more than or equal to 0.1 and less than or equal to 1, c is more than or equal to 0.5 and less than or equal to 4, and d is more than or equal to 0.01 and less than or equal to 0.05.
Table 1: compositions of microwave dielectric ceramic materials for the examples
Example 1
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 1.0g of the calcined powder obtained in the step S4, 1.5g of 99.5% zirconium dioxide, 0.1g of 99.9% niobium pentoxide, and 0.05g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried, and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 2
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 2.5g of the calcined powder obtained in the step S4, 2.5g of 99.5% zirconium dioxide, 0.2g of 99.9% niobium pentoxide and 0.03g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 3
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 3.5g of the calcined powder obtained in the step S4, 0.5g of 99.5% zirconium dioxide, 0.5g of 99.9% niobium pentoxide, and 0.01g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried, and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 4
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 4.5g of the calcined powder obtained in the step S4, 0.5g of 99.5% zirconium dioxide, 0.7g of 99.9% niobium pentoxide, and 0.01g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried, and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering for 4 hours at the temperature of 1425 ℃ to obtain the final microwave dielectric ceramic material.
Example 5
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 4.5g of the calcined powder obtained in the step S4, 0.5g of 99.5% zirconium dioxide, 1.0g of 99.9% niobium pentoxide, and 0.05g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried, and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1400 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 6
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 1.0g of the calcined powder obtained in the step S4, 4.0g of 99.5% zirconium dioxide, 0.7g of 99.9% niobium pentoxide, and 0.05g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried, and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 7
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 2.5g of the calcined powder obtained in the step S4, 3.5g of 99.5% zirconium dioxide, 0.7g of 99.9% niobium pentoxide and 0.03g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 8
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 3.5g of the calcined powder obtained in the step S4, 2.0g of 99.5% zirconium dioxide, 0.7g of 99.9% niobium pentoxide, and 0.01g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried, and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 9
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 4.5g of the calcined powder obtained in the step S4, 1.5g of 99.5% zirconium dioxide, 0.7g of 99.9% niobium pentoxide and 0.03g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering for 4 hours at the temperature of 1425 ℃ to obtain the final microwave dielectric ceramic material.
Example 10
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 5.50g of the calcined powder obtained in the step S4, 0.5g of 99.5% zirconium dioxide, 0.5g of 99.9% niobium pentoxide, and 0.05g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried, and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1400 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 11
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 1.5g of the calcined powder obtained in the step S4, 2.5g of 99.5% zirconium dioxide, 1.0g of 99.9% niobium pentoxide, and 0.01g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried, and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 12
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 2.0g of the calcined powder obtained in the step S4, 2.0g of 99.5% zirconium dioxide, 1.0g of 99.9% niobium pentoxide and 0.03g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 13
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 2.5g of the calcined powder obtained in the step S4, 1.5g of 99.5% zirconium dioxide, 0.7g of 99.9% niobium pentoxide and 0.03g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 14
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 2.5g of the calcined powder obtained in the step S4, 1.5g of 99.5% zirconium dioxide, 0.5g of 99.9% niobium pentoxide and 0.01g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 15
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 2.5g of the calcined powder obtained in the step S4, 1.5g of 99.5% zirconium dioxide, 0.5g of 99.9% niobium pentoxide and 0.05g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Example 16
S1, preparing 99.5% calcium carbonate, 99.9% lanthanum oxide, 99.5% aluminum oxide and 99.5% titanium dioxide according to the weight percentages of 33.92 wt%, 27.06 wt%, 29.72 wt% and 9.30 wt%, respectively, and mixing the obtained mixture by using zirconium dioxide balls as a ball milling medium and deionized water as a solvent according to the following ratio: ball milling media: solvent 1: 5: 2 for 6 hours, drying and sieving by a sieve of 80 meshes to obtain dry powder.
S2: and (4) placing the dried powder obtained in the step (S1) in a crucible, presintering at 1200 ℃ and preserving heat for 4 hours to obtain presintering powder.
S3: taking 99% basic magnesium carbonate, 99.5% aluminum oxide and 99.5% silicon dioxide as raw materials, respectively blending according to the weight percentages of 38.92%, 24.70% and 36.38%, taking zirconium dioxide balls as ball milling media and deionized water as a solvent to obtain a mixture, and mixing the raw materials according to the following ratio: ball milling medium: solvent 1: 5: 3 for 5 hours, drying and sieving by a 120-mesh sieve to obtain dry powder.
S4: and (4) placing the dried powder obtained in the step (S3) in a crucible, presintering at 1350 ℃ and preserving heat for 4 hours to obtain presintering powder.
S5: 100g of the calcined powder obtained in the step S2, 2.5g of the calcined powder obtained in the step S4, 1.5g of 99.5% zirconium dioxide, 1.0g of 99.9% niobium pentoxide, and 0.03g of 99.5% manganese carbonate were weighed, mixed and ball-milled for 6 hours, dried, and sieved with a 80-mesh sieve to obtain a dried powder.
S6: and (4) mixing the dried powder obtained in the step (S5) with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body.
S7: and (4) placing the green body obtained in the step S6 on a setter plate, and sintering at 1450 ℃ for 4 hours to obtain the final microwave dielectric ceramic material.
Table 2: the microwave dielectric ceramic material prepared by the above-listed embodiment of the invention has the performance parameters
Thermal shock test: 10 samples fired in step S7 were taken from each example and placed at a temperature T1The temperature of the vacuum drying oven is kept for half an hour, then the vacuum drying oven is quickly taken out and placed into an ice water compound for 10 minutes, then a sample is taken out, wiped to be dry and placed into a fuchsin solution for soaking for 10 minutes, the sample is taken out and observed whether cracks appear under an optical microscope, and the critical thermal shock temperature difference indicates that the 10 samples do not have the maximum temperature T of cracks after a thermal shock test1。
The microwave dielectric ceramic material prepared by the invention has the thermal shock resistance temperature difference of more than 100 ℃, the thermal shock resistance temperature difference of the existing microwave ceramic material is below 70 ℃, the improvement is 42.9%, and simultaneously, the excellent microwave dielectric property is still maintainedfThe microwave dielectric ceramic material is between-10 ppm/DEG C and +10 ppm/DEG C, so that the thermal shock resistance of the microwave dielectric ceramic material provided by the invention is greatly improved.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes be made by those skilled in the art without departing from the spirit and technical spirit of the present invention as set forth in the appended claims.
Claims (9)
1. A microwave dielectric ceramic material for a 5G base station is characterized by comprising the following components in a general formula: ca1-xLaxTi1-yAlyO3+a wt％Mg2Al4Si5O18+b wt％Nb2O5+c wt％ZrO2+ d wt% MnO, where x and y are molar content ratio, x is 0.2-0.4, and y is 0.2-0.4; a, b, c, d are in Ca1-xLaxTi1-yAlyO3The value ranges of the mass percentage contents are respectively as follows: a is more than or equal to 0.01 and less than or equal to 7, b is more than or equal to 0.001 and less than or equal to 2, c is more than or equal to 0.001 and less than or equal to 5, and d is more than or equal to 0.001 and less than or equal to 0.5.
2. The microwave dielectric ceramic material for the 5G base station according to claim 1, wherein the value ranges of a, b, c and d are respectively as follows: a is more than or equal to 1 and less than or equal to 5.5, b is more than or equal to 0.1 and less than or equal to 1, c is more than or equal to 0.5 and less than or equal to 4, and d is more than or equal to 0.01 and less than or equal to 0.05.
3. A method for preparing a microwave dielectric ceramic material for a 5G base station according to claim 1 or 2, comprising the following steps:
s1: calcium carbonate, lanthanum oxide, titanium dioxide and aluminum oxide are taken as raw materials, and Ca is expressed according to a general formula1-xLaxTi1-yAlyO3The molar content ratio of x is more than or equal to 0.2 and less than or equal to 0.4, and y is more than or equal to 0.2 and less than or equal to 0.4, and after grinding and mixing, drying to obtain dry powder;
s2: placing the dried powder obtained in the step S1 in a crucible for presintering to obtain presintering powder;
s3: basic magnesium carbonate, aluminum oxide and silicon dioxide are used as raw materials, and the formula is Mg2Al4Si5O18The molar content ratio of the components is mixed, ground and mixedAfter combination, drying to obtain dry powder;
s4: placing the dried powder obtained in the step S3 in a crucible for presintering to obtain presintering powder;
s5: mixing and grinding the pre-sintered powder obtained in the step S2, the pre-sintered powder obtained in the step S4, zirconium dioxide, niobium pentoxide and manganese carbonate according to the general formula of the ceramic material, and drying to obtain dry powder;
s6: mixing the dry powder obtained in the step S5 with a polyvinyl alcohol aqueous solution, granulating, and putting the granules into a forming die for dry pressing and forming to obtain a green body;
s7: and (5) placing the green body obtained in the step S6 on a setter plate to be sintered to obtain the final microwave dielectric ceramic material.
4. The method for preparing the microwave dielectric ceramic material for the 5G base station according to claim 3, wherein the concentrations of the adopted raw materials are as follows: 99.5% of calcium carbonate, 99.9% of lanthanum oxide, 99.5% of titanium dioxide, 99.5% of aluminum oxide, 99.5% of zirconium dioxide, 99.9% of niobium pentoxide, 99% of basic magnesium carbonate, 99.5% of silicon dioxide and 99.5% of manganese carbonate.
5. The method for preparing a microwave dielectric ceramic material for a 5G base station according to claim 3, wherein the mixture obtained by blending in the step S1 and the mixture obtained by blending in the step S3 are prepared by using zirconium dioxide balls as ball milling media and deionized water as solvents respectively, according to the following formula: ball milling medium: solvent 1: 5: grinding for 4-8 hours according to the weight ratio of 1-3, drying and sieving by a sieve of 40-120 meshes to obtain dry powder.
6. The method for preparing a microwave dielectric ceramic material for a 5G base station according to claim 3, wherein the step S2 is to place the dried powder obtained in the step S1 in a crucible, presintering at 1100-1300 ℃ and preserving heat for 2-5 hours to obtain presintered powder; and step S4, pre-sintering the dried powder obtained in step S3 at 1200-1400 ℃ and keeping the temperature for 2-5 hours to obtain pre-sintered powder.
7. The preparation method of the microwave dielectric ceramic material for the 5G base station as claimed in claim 3, wherein the mixture obtained by blending in the step S5 is ball-milled for 2-6 hours, dried and sieved by a 40-120 mesh sieve to obtain dried powder.
8. The method for preparing a microwave dielectric ceramic material for a 5G base station according to claim 3, wherein the granulation size in the step S6 is 100-200 meshes.
9. The method for preparing a microwave dielectric ceramic material for a 5G base station as claimed in claim 3, wherein the green body in the step S7 is sintered at 1350-1550 ℃ for 2-6 hours to obtain a final microwave dielectric ceramic material.
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| JP2003026471A (en) * | 2001-07-12 | 2003-01-29 | Ube Electronics Ltd | Dielectric porcelain composition for high frequency and method of manufacturing the same |
| CN103172367A (en) * | 2011-12-22 | 2013-06-26 | 深圳市大富科技股份有限公司 | Preparation method of microwave dielectric ceramic material |
| CN105000884A (en) * | 2015-08-18 | 2015-10-28 | 广东国华新材料科技股份有限公司 | Microwave dielectric ceramic material as well as preparation method and application thereof |
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| JP2003026471A (en) * | 2001-07-12 | 2003-01-29 | Ube Electronics Ltd | Dielectric porcelain composition for high frequency and method of manufacturing the same |
| CN103172367A (en) * | 2011-12-22 | 2013-06-26 | 深圳市大富科技股份有限公司 | Preparation method of microwave dielectric ceramic material |
| CN105000884A (en) * | 2015-08-18 | 2015-10-28 | 广东国华新材料科技股份有限公司 | Microwave dielectric ceramic material as well as preparation method and application thereof |
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