CN105000884A - Microwave dielectric ceramic material as well as preparation method and application thereof - Google Patents
Microwave dielectric ceramic material as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN105000884A CN105000884A CN201510508571.0A CN201510508571A CN105000884A CN 105000884 A CN105000884 A CN 105000884A CN 201510508571 A CN201510508571 A CN 201510508571A CN 105000884 A CN105000884 A CN 105000884A
- Authority
- CN
- China
- Prior art keywords
- dielectric ceramic
- microwave dielectric
- ceramic materials
- microwave
- burning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- 238000004891 communication Methods 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims abstract description 3
- 239000004576 sand Substances 0.000 claims description 67
- 238000003801 milling Methods 0.000 claims description 39
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000007599 discharging Methods 0.000 claims description 32
- 238000005507 spraying Methods 0.000 claims description 31
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 16
- 239000004408 titanium dioxide Substances 0.000 claims description 16
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 10
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 10
- 239000003595 mist Substances 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 68
- 150000001875 compounds Chemical class 0.000 description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- 239000008367 deionised water Substances 0.000 description 30
- 229910021641 deionized water Inorganic materials 0.000 description 30
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 28
- 238000001694 spray drying Methods 0.000 description 28
- 239000004372 Polyvinyl alcohol Substances 0.000 description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 238000005469 granulation Methods 0.000 description 14
- 230000003179 granulation Effects 0.000 description 14
- 238000010298 pulverizing process Methods 0.000 description 14
- 238000007493 shaping process Methods 0.000 description 14
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 9
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 9
- 238000011161 development Methods 0.000 description 5
- 238000010835 comparative analysis Methods 0.000 description 4
- 238000010295 mobile communication Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000004500 asepsis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention belongs to the field of new materials and microwave communication, and particularly relates to a microwave dielectric ceramic material as well as a preparation method and application thereof. The principal crystalline phase of the microwave medium ceramic material adopts the structure of xCaTiO3-(1-x)ReAO3; Re refers to at least one of La, Ns and Sm, and A refers to at least one of Al and Ga; x is less than or equal to 1 and is greater than or equal to 0; the microwave dielectric ceramic material further comprises a modified additive. According to the invention, the microwave dielectric ceramic material is prepared through steps of compounding, sanding, presintering and adding the modified additive, sanding, pelletizating, pressing for formation and sintering. The material has the characteristics of low cost and excellent microwave dielectric property, is high in electric inductivity, high in Q, has a frequency temperature coefficient close to zero temperature excursion and is continuously adjustable in accessories within a certain range, and can be used for manufacturing microwave components such as dielectric resonators, all-dielectric filters, cavity filters, antennas and the like in a communication system.
Description
Technical field
The invention belongs to novel material and field of microwave communication, be specifically related to a kind of microwave dielectric ceramic materials and preparation method thereof and application.
Background technology
As mobile communication technology of future generation, LTE becomes the essential road of the following communication network development of communication operator.But numerous challenge Ye Shi operators such as frequency spectrum resource is nervous, highly energy-consuming, high cost are faced with severeer cost pressure.2015, China can be public mobile communication and plans about 1000MHz bandwidth spectrum resource, but the 1360MHz total bandwidth need of Academy of Telecom Research of distance Ministry of Industry and Information estimation also has about 300MHz breach, and frequency spectrum resource is nervous, improves the availability of frequency spectrum and becomes the task of top priority.
Microwave-medium ceramics is the new function electronic ceramics developed rapidly over nearly 30 years, and it has, and loss is low, frequency-temperature coefficient is little, specific inductivity high.Along with the fast development of mobile communication, particularly forth generation mobile communications network (4G) the TD-LTE epoch arrive.The demand being applied to the microwave dielectric material of the microwave devices such as dielectric resonator, all dielectric wave filter, cavity body filter, antenna is also growing.Towards miniaturization, high frequency, low cost and eco-friendly future development, microwave-medium ceramics is had higher requirement.
Summary of the invention
In order to overcome the shortcoming and defect of prior art, primary and foremost purpose of the present invention is to provide a kind of microwave dielectric ceramic materials, advantage that this microwave dielectric ceramic materials has high-k, high q-factor, frequency-temperature coefficient is adjustable and preparation cost is cheap etc., can meet the demand for development of microwave device miniaturization, high frequency, low cost.
Another object of the present invention is to the preparation method that above-mentioned microwave dielectric ceramic materials is provided.
Another object of the present invention is the application providing above-mentioned microwave dielectric ceramic materials.
Object of the present invention is achieved through the following technical solutions:
A kind of microwave dielectric ceramic materials, the structure of principal crystalline phase is xCaTiO
3-(1-x) ReAO
3; Wherein, Re is at least one in La, Nd and Sm, and A is at least one in Al and Ga; 0≤x≤1;
Described microwave dielectric ceramic materials also comprises property-modifying additive;
Described property-modifying additive is preferably ZrO
2and MnO
2in at least one;
The total content of described property-modifying additive in microwave dielectric ceramic materials is 0 ~ 2.0wt%;
The total content of described property-modifying additive in microwave dielectric ceramic materials is preferably 0.1wt% ~ 2.0wt%;
The structure xCaTiO of described microwave dielectric ceramic materials principal crystalline phase
3-(1-x) ReAO
3the value of middle x is preferably 0.5 ~ 0.8;
The preparation method of described microwave dielectric ceramic materials, comprises the steps:
(1) get at least one in calcium carbonate, titanium dioxide, rare earth oxide and aluminum oxide and gallium oxide according to the stoichiometric ratio of principal crystalline phase structural formula, sand milling makes to mix;
(2) discharging, spraying dry, then carries out pre-burning at the temperature of 1000 ~ 1300 DEG C;
(3) pulverize, do not add or add property-modifying additive, sand milling makes to mix again;
(4) discharging, mist projection granulating, sieves, compression moulding;
(5) sinter at the temperature of 1300 ~ 1600 DEG C, obtain microwave dielectric ceramic materials;
Rare earth oxide described in step (1) is at least one in lanthanum trioxide, Neodymium trioxide and Samarium trioxide;
The condition optimization of the sand milling described in step (1) is: be ball-milling medium with deionized water, and take zirconia ball as abrading-ball, the sand milling time is 0.5 ~ 2 hour;
The time of the pre-burning described in step (2) is preferably 2 ~ 10 hours;
Spray-dired temperature described in step (2) is preferably 100 ~ 300 DEG C;
The condition optimization of the sand milling described in step (3) is: be ball-milling medium with deionized water, and take zirconia ball as abrading-ball, the sand milling time is 0.5 ~ 10 hour;
Mist projection granulating preferred operations described in step (4) is: the polyvinyl alcohol water solution adding 1 ~ 8wt%, then spraying dry; Described spray-dired temperature is preferably 100 ~ 300 DEG C;
Sieving described in step (4) was preferably 40 ~ 300 mesh sieves;
The time of the sintering described in step (5) is preferably 2 ~ 15 hours;
The application of described microwave dielectric ceramic materials in novel material and field of microwave communication;
The present invention has following advantage and effect relative to prior art:
(1) the microwave dielectric ceramic materials homogeneity adopting the mode such as sand milling and mist projection granulating to prepare is better, and performance is more excellent;
(2) microwave dielectric ceramic materials that the present invention prepares has good microwave dielectric property: DIELECTRIC CONSTANT ε=27 ~ 55, and adjustable within the scope of this; Quality factor q f=22000 ~ 80000GHz (resonant frequency f=3 ~ 6GHz); Frequency-temperature coefficient τ f=-62 ~ 55ppm/ DEG C, and adjustable within the scope of this;
(3) by adjustment formula, collective frequency temperature factor (i.e. high temperature frequency-temperature coefficient and the low temperature frequency-temperature coefficient sum) continuously adjustabe within the scope of-10ppm/ DEG C to+10ppm/ DEG C of microwave dielectric ceramic materials can be realized;
(4) raw material of the present invention is cheap and easy to get, asepsis environment-protecting;
(5) preparation technology of the present invention is simple, without the need to specific installation and stringent process conditions, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the microwave dielectric ceramic materials that embodiment 6 prepares.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
In embodiment, the dielectric properties of pottery record under 3 ~ 6GHz frequency.
Embodiment 1
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 2.91kg, titanium dioxide 2.32kg, lanthanum trioxide 3.32kg, Samarium trioxide 0kg, Neodymium trioxide 7.99kg, aluminum oxide 3.46kg, gallium oxide 0kg, is mixed to get the first compound; By the first compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 5h at the temperature of 1250 DEG C, temperature rise rate is 3 DEG C/min, and furnace cooling obtains the first Preburning material;
(3) get the first Preburning material 16kg, property-modifying additive zirconium white 0g and manganese oxide 0g after pulverizing, be mixed to get compound after the first pre-burning; By compound, deionized water and zirconia ball after the first pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, after adopting spray-drying tower 220 DEG C of spraying dry, crosses 40 mesh sieves, obtains the first granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1450 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
Embodiment 2
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 2.52kg, titanium dioxide 2.01kg, lanthanum trioxide 2.87kg, Samarium trioxide 5.12kg, Neodymium trioxide 1.98kg, aluminum oxide 0kg, gallium oxide 5.5kg, is mixed to get the second compound; By the second compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 5h at the temperature of 1250 DEG C, temperature rise rate is 3 DEG C/min, and furnace cooling obtains the second Preburning material;
(3) get the second Preburning material 16kg, property-modifying additive zirconium white 40g and manganese oxide 80g after pulverizing, be mixed to get compound after the second pre-burning; By compound, deionized water and zirconia ball after the second pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, after adopting spray-drying tower 220 DEG C of spraying dry, crosses 40 mesh sieves, obtains the second granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1550 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
Embodiment 3
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 5.61kg, titanium dioxide 4.47kg, lanthanum trioxide 3.73kg, Samarium trioxide 0kg, Neodymium trioxide 3.85kg, aluminum oxide 2.34kg, gallium oxide 0kg, is mixed to get the 3rd compound; By the 3rd compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 5h at the temperature of 1250 DEG C, temperature rise rate is 3 DEG C/min, furnace cooling, obtains the 3rd Preburning material;
(3) get the 3rd Preburning material 16kg, property-modifying additive zirconium white 40g and manganese oxide 80g after pulverizing, be mixed to get compound after the 3rd pre-burning; By compound, deionized water and zirconia ball after the 3rd pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the 3rd granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1450 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
Embodiment 4
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 5.07kg, titanium dioxide 4.05kg, lanthanum trioxide 3.38kg, Samarium trioxide 3.62kg, Neodymium trioxide 0kg, aluminum oxide 0kg, gallium oxide 3.89kg, is mixed to get the 4th compound; By the 4th compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 5h at the temperature of 1250 DEG C, temperature rise rate is 3 DEG C/min, furnace cooling, obtains the 4th Preburning material;
(3) get the 4th Preburning material 16kg, property-modifying additive zirconium white 0g and manganese oxide 0g after pulverizing, be mixed to get compound after the 4th pre-burning; By compound, deionized water and zirconia ball after the 4th pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the 4th granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1550 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
Embodiment 5
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 6.88kg, titanium dioxide 5.49kg, lanthanum trioxide 2.4kg, Samarium trioxide 0kg, Neodymium trioxide 2.48kg, aluminum oxide 0kg, gallium oxide 2.76kg, is mixed to get the 5th compound; By the 5th compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 5h at the temperature of 1250 DEG C, temperature rise rate is 3 DEG C/min, furnace cooling, obtains the 5th Preburning material;
(3) get the 5th Preburning material 16kg, property-modifying additive zirconium white 0g and manganese oxide 80g after pulverizing, be mixed to get compound after the 5th pre-burning; By compound, deionized water and zirconia ball after the 5th pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the 5th granulation material; Then adopt the forming pressure of 120MPa shaping
(5) at the temperature of 1450 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
Embodiment 6
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 7.3kg, titanium dioxide 5.83kg, lanthanum trioxide 2.55kg, Samarium trioxide 2.73kg, Neodymium trioxide 0kg, aluminum oxide 1.59kg, gallium oxide 0kg, is mixed to get the 6th compound; By the 6th compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 5h at the temperature of 1250 DEG C, temperature rise rate is 3 DEG C/min, furnace cooling, obtains the 6th Preburning material;
(3) get the 6th Preburning material 16kg, property-modifying additive zirconium white 40g and manganese oxide 0g after pulverizing, be mixed to get compound after the 6th pre-burning; By compound, deionized water and zirconia ball after the 6th pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the 6th granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1550 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.Fig. 1 is the SEM figure of this microwave dielectric ceramic materials.
Embodiment 7
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 8.86kg, titanium dioxide 7.07kg, lanthanum trioxide 0.76kg, Samarium trioxide 0kg, Neodymium trioxide 1.84kg, aluminum oxide 0kg, gallium oxide 1.46kg, is mixed to get the 7th compound; By the 7th compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 5h at the temperature of 1250 DEG C, temperature rise rate is 3 DEG C/min, furnace cooling, obtains the 7th Preburning material;
(3) get the 7th Preburning material 16kg, property-modifying additive zirconium white 40g and manganese oxide 0g after pulverizing, be mixed to get compound after the 7th pre-burning; By compound, deionized water and zirconia ball after the 7th pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the 7th granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1450 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
Embodiment 8
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 9.14kg, titanium dioxide 7.3kg, lanthanum trioxide 0.79kg, Samarium trioxide 1.41kg, Neodymium trioxide 0.54kg, aluminum oxide 0.82kg, gallium oxide 0kg, is mixed to get the 8th compound; By described 8th compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 5h at the temperature of 1250 DEG C, temperature rise rate is 3 DEG C/min, furnace cooling, obtains the 8th Preburning material;
(3) get the 8th Preburning material 16kg, property-modifying additive zirconium white 0g and manganese oxide 80g after pulverizing, be mixed to get compound after the 8th pre-burning; By compound, deionized water and zirconia ball after the 8th pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the 8th granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1550 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
The comparative analysis of table 1 embodiment 1 ~ 8 reactant consumption
The microwave dielectric property comparative analysis of the microwave dielectric ceramic materials that table 2 embodiment 1 ~ 8 prepares
Embodiment 9
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 7.37kg, titanium dioxide 5.88kg, lanthanum trioxide 5.14kg, aluminum oxide 1.63kg, is mixed to get the 9th compound; By the 9th compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 0.5h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 2h at the temperature of 1000 DEG C, temperature rise rate is 3 DEG C/min, furnace cooling, obtains the 9th Preburning material;
(3) get the 9th Preburning material 16kg after pulverizing, property-modifying additive manganese oxide 16g, be mixed to get compound after the 9th pre-burning; By compound, deionized water and zirconia ball after the 9th pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the 9th granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1550 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
Embodiment 10
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 7.37kg, titanium dioxide 5.88kg, lanthanum trioxide 5.14kg, aluminum oxide 1.63kg, is mixed to get the tenth compound; By the tenth compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 9h at the temperature of 1100 DEG C, temperature rise rate is 3 DEG C/min, furnace cooling, obtains the tenth Preburning material;
(3) get the tenth Preburning material 16kg after pulverizing, property-modifying additive manganese oxide 16g, be mixed to get compound after the tenth pre-burning; By compound, deionized water and zirconia ball after the tenth pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 0.5h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the tenth granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1550 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
Embodiment 11
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 7.37kg, titanium dioxide 5.88kg, lanthanum trioxide 5.14kg, aluminum oxide 1.63kg, is mixed to get the 11 compound; By the 11 compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 2h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 2h at the temperature of 1300 DEG C, temperature rise rate is 3 DEG C/min, and furnace cooling obtains the 11 Preburning material;
(3) get the 11 Preburning material 16kg after pulverizing, property-modifying additive manganese oxide 16g, be mixed to get compound after the 11 pre-burning; By compound, deionized water and zirconia ball after the 11 pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the 11 granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1550 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
Embodiment 12
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 7.37kg, titanium dioxide 5.88kg, lanthanum trioxide 5.14kg, aluminum oxide 1.63kg, is mixed to get the 11 compound; By the 11 compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 0.5h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 10h at the temperature of 1300 DEG C, temperature rise rate is 3 DEG C/min, and furnace cooling obtains the 11 Preburning material;
(3) get the 11 Preburning material 16kg after pulverizing, property-modifying additive manganese oxide 16g, be mixed to get compound after the 11 pre-burning; By compound, deionized water and zirconia ball after the 11 pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 1h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the 11 granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1550 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
Embodiment 13
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 7.37kg, titanium dioxide 5.88kg, lanthanum trioxide 5.14kg, aluminum oxide 1.63kg, is mixed to get the 11 compound; By the 11 compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 0.5h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 10h at the temperature of 1300 DEG C, temperature rise rate is 3 DEG C/min, and furnace cooling obtains the 11 Preburning material;
(3) get the 11 Preburning material 16kg after pulverizing, property-modifying additive manganese oxide 16g, be mixed to get compound after the 11 pre-burning; By compound, deionized water and zirconia ball after the 11 pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 7h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the 11 granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1550 DEG C, sinter 5 hours, obtain microwave dielectric ceramic materials.
Embodiment 14
(1) according to principal crystalline phase structural formula: xCaTiO
3-(1-x) ReAO
3stoichiometric ratio takes calcium carbonate 7.37kg, titanium dioxide 5.88kg, lanthanum trioxide 5.14kg, aluminum oxide 1.63kg, is mixed to get the 11 compound; By the 11 compound, deionized water and zirconia ball with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 0.5h;
(2) discharging, adopt spray-drying tower 220 DEG C of spraying dry, then pre-burning 10h at the temperature of 1300 DEG C, temperature rise rate is 3 DEG C/min, and furnace cooling obtains the 11 Preburning material;
(3) get the 11 Preburning material 16kg after pulverizing, property-modifying additive manganese oxide 16g, be mixed to get compound after the 11 pre-burning; By compound, deionized water and zirconia ball after the 11 pre-burning with the mass ratio of 1:2:0.5, make to mix with sand mill sand milling 10h;
(4) discharging, adds the polyvinyl alcohol water solution of 1.5wt%, and after adopting spray-drying tower 220 DEG C of spraying dry, sieve 40 orders, obtains the 11 granulation material; Then adopt the forming pressure of 120MPa shaping;
(5) at the temperature of 1550 DEG C, sinter 15 hours, obtain microwave dielectric ceramic materials.
The comparative analysis of table 3 embodiment 9 ~ 14 reaction conditions
| Numbering | Calcined temperature (DEG C) | Burn-in time (h) | Sand milling time (h) before pre-burning | Sand milling time (h) after pre-burning |
| Embodiment 9 | 1000 | 2 | 0.5 | 1 |
| Embodiment 10 | 1100 | 9 | 1 | 0.5 |
| Embodiment 11 | 1300 | 2 | 2 | 1 |
| Embodiment 12 | 1300 | 10 | 0.5 | 1 |
| Embodiment 13 | 1300 | 10 | 0.5 | 7 |
| Embodiment 14 | 1300 | 10 | 0.5 | 10 |
The microwave dielectric property comparative analysis of the microwave dielectric ceramic materials that table 4 embodiment 9 ~ 14 prepares
From table 1 ~ 4: the microwave dielectric ceramic materials that the present invention prepares has low cost and good microwave dielectric property: DIELECTRIC CONSTANT ε=27 ~ 55, and adjustable within the scope of this; Quality factor q f=22000 ~ 80000GHz (resonant frequency f=3 ~ 6GHz); Frequency-temperature coefficient τ f=-62 ~ 55ppm/ DEG C, and adjustable within the scope of this; The demand for development of microwave device miniaturization, high frequency can be met, can be used for manufacturing the microwave device such as dielectric resonator, all dielectric wave filter, cavity body filter, antenna in communication system.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a microwave dielectric ceramic materials, is characterized in that: the structure of principal crystalline phase is xCaTiO
3-(1-x) ReAO
3; Wherein, Re is at least one in La, Nd and Sm, and A is at least one in Al and Ga; 0≤x≤1.
2. microwave dielectric ceramic materials according to claim 1, is characterized in that:
Described microwave dielectric ceramic materials also comprises property-modifying additive.
3. microwave dielectric ceramic materials according to claim 2, is characterized in that:
Described property-modifying additive is ZrO
2and MnO
2in at least one.
4. microwave dielectric ceramic materials according to claim 2, is characterized in that:
The described total content of property-modifying additive in microwave dielectric ceramic materials is 0 ~ 2.0wt%.
5. microwave dielectric ceramic materials according to claim 4, is characterized in that:
The total content of described property-modifying additive in microwave dielectric ceramic materials is 0.1wt% ~ 2.0wt%.
6. microwave dielectric ceramic materials according to claim 1, is characterized in that:
The structure xCaTiO of principal crystalline phase in described microwave dielectric ceramic materials
3-(1-x) ReAO
3the value of middle x is 0.5 ~ 0.8.
7. the preparation method of the microwave dielectric ceramic materials described in any one of claim 1 ~ 6, is characterized in that comprising the steps:
(1) get at least one in calcium carbonate, titanium dioxide, rare earth oxide and aluminum oxide and gallium oxide according to the stoichiometric ratio of principal crystalline phase structural formula, sand milling makes to mix;
(2) discharging, spraying dry, then carries out pre-burning at the temperature of 1000 ~ 1300 DEG C;
(3) pulverize, do not add or add property-modifying additive, sand milling makes to mix again;
(4) discharging, mist projection granulating, sieves, compression moulding;
(5) sinter at the temperature of 1300 ~ 1600 DEG C, obtain microwave dielectric ceramic materials.
8. the preparation method of microwave dielectric ceramic materials according to claim 7, is characterized in that:
The time of the pre-burning described in step (2) is 2 ~ 10 hours.
9. the preparation method of microwave dielectric ceramic materials according to claim 7, is characterized in that:
The time of the sintering described in step (5) is 2 ~ 15 hours.
10. the application of the microwave dielectric ceramic materials described in any one of claim 1 ~ 6 in novel material and field of microwave communication.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510508571.0A CN105000884A (en) | 2015-08-18 | 2015-08-18 | Microwave dielectric ceramic material as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510508571.0A CN105000884A (en) | 2015-08-18 | 2015-08-18 | Microwave dielectric ceramic material as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105000884A true CN105000884A (en) | 2015-10-28 |
Family
ID=54373803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510508571.0A Pending CN105000884A (en) | 2015-08-18 | 2015-08-18 | Microwave dielectric ceramic material as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105000884A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924151A (en) * | 2016-04-20 | 2016-09-07 | 苏州艾福电子通讯股份有限公司 | Microwave dielectric ceramic powder, preparation method thereof, microwave dielectric ceramic and microwave component |
| CN106083026A (en) * | 2016-06-17 | 2016-11-09 | 航天材料及工艺研究所 | A kind of ultralow temperature molten salt preparation method of microwave dielectric nano-ceramic powder aluminic acid neodymium |
| CN107188557A (en) * | 2017-06-01 | 2017-09-22 | 电子科技大学 | A kind of microwave dielectric ceramic materials and preparation method thereof |
| CN110156465A (en) * | 2019-06-10 | 2019-08-23 | 南京信息工程大学 | A kind of preparation method of medium permittivity ceramic dielectric resonator material |
| CN110451952A (en) * | 2019-09-12 | 2019-11-15 | 无锡鑫圣慧龙纳米陶瓷技术有限公司 | A kind of low loss and high strength microwave-medium ceramics and preparation method thereof |
| CN110734284A (en) * | 2019-11-11 | 2020-01-31 | 深圳顺络电子股份有限公司 | medium high Q microwave medium ceramic material and preparation method thereof |
| CN111138193A (en) * | 2020-01-03 | 2020-05-12 | 山东国瓷功能材料股份有限公司 | Microwave dielectric ceramic material with medium dielectric constant and preparation method and application thereof |
| CN111377710A (en) * | 2018-12-31 | 2020-07-07 | 深圳市大富科技股份有限公司 | Microwave dielectric ceramic material and preparation method of dielectric ceramic block |
| CN113105230A (en) * | 2021-03-18 | 2021-07-13 | 摩比天线技术（深圳）有限公司 | Microwave dielectric ceramic material for 5G base station and preparation method thereof |
| CN116969760A (en) * | 2023-08-01 | 2023-10-31 | 陕西华星电子开发有限公司 | Ca-Sm-Al-Ti-based microwave dielectric ceramic material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102318135A (en) * | 2010-11-01 | 2012-01-11 | 华为技术有限公司 | Production Method of Microwave Dielectric Resonator and Microwave Dielectric Duplexer |
| CN102390995A (en) * | 2011-08-17 | 2012-03-28 | 武汉凡谷电子技术股份有限公司 | Microwave dielectric ceramic material and production process thereof |
| CN102718476A (en) * | 2012-05-30 | 2012-10-10 | 深圳光启创新技术有限公司 | Dielectric ceramic |
| CN103408298A (en) * | 2013-08-05 | 2013-11-27 | 无锡鑫圣慧龙纳米陶瓷技术有限公司 | Microwave dielectric ceramic material applicable to low temperature sintering and preparation method of microwave dielectric ceramic material |
| CN103626488A (en) * | 2013-11-28 | 2014-03-12 | 广东风华高新科技股份有限公司 | Microwave ceramic dielectric material and preparation method thereof |
-
2015
- 2015-08-18 CN CN201510508571.0A patent/CN105000884A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102318135A (en) * | 2010-11-01 | 2012-01-11 | 华为技术有限公司 | Production Method of Microwave Dielectric Resonator and Microwave Dielectric Duplexer |
| CN102390995A (en) * | 2011-08-17 | 2012-03-28 | 武汉凡谷电子技术股份有限公司 | Microwave dielectric ceramic material and production process thereof |
| CN102718476A (en) * | 2012-05-30 | 2012-10-10 | 深圳光启创新技术有限公司 | Dielectric ceramic |
| CN103408298A (en) * | 2013-08-05 | 2013-11-27 | 无锡鑫圣慧龙纳米陶瓷技术有限公司 | Microwave dielectric ceramic material applicable to low temperature sintering and preparation method of microwave dielectric ceramic material |
| CN103626488A (en) * | 2013-11-28 | 2014-03-12 | 广东风华高新科技股份有限公司 | Microwave ceramic dielectric material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| BOSTJAN JANCAR ET AL.: "Microwave Dielectric Properties and Microstructural Characteristics of Aliovalently Doped Perovskite Ceramics Based on CaTiO3", 《KEY ENGINEERING MATERIALS》 * |
| 曹良足等: "CaTiO3-(La,Nd)AlO3微波介质陶瓷的研究与应用", 《电子元件与材料》 * |
| 梁飞等: "0.7CaTiO3-0.3(LaxNd1-x)AlO3微波介质陶瓷的研究", 《电子元件与材料》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924151A (en) * | 2016-04-20 | 2016-09-07 | 苏州艾福电子通讯股份有限公司 | Microwave dielectric ceramic powder, preparation method thereof, microwave dielectric ceramic and microwave component |
| CN106083026A (en) * | 2016-06-17 | 2016-11-09 | 航天材料及工艺研究所 | A kind of ultralow temperature molten salt preparation method of microwave dielectric nano-ceramic powder aluminic acid neodymium |
| CN107188557A (en) * | 2017-06-01 | 2017-09-22 | 电子科技大学 | A kind of microwave dielectric ceramic materials and preparation method thereof |
| CN111377710A (en) * | 2018-12-31 | 2020-07-07 | 深圳市大富科技股份有限公司 | Microwave dielectric ceramic material and preparation method of dielectric ceramic block |
| CN110156465B (en) * | 2019-06-10 | 2021-12-28 | 南京信息工程大学 | Preparation method of ceramic dielectric resonator material with medium dielectric constant |
| CN110156465A (en) * | 2019-06-10 | 2019-08-23 | 南京信息工程大学 | A kind of preparation method of medium permittivity ceramic dielectric resonator material |
| CN110451952A (en) * | 2019-09-12 | 2019-11-15 | 无锡鑫圣慧龙纳米陶瓷技术有限公司 | A kind of low loss and high strength microwave-medium ceramics and preparation method thereof |
| CN110451952B (en) * | 2019-09-12 | 2022-01-25 | 无锡鑫圣慧龙纳米陶瓷技术有限公司 | Low-loss high-strength microwave dielectric ceramic and preparation method thereof |
| CN110734284A (en) * | 2019-11-11 | 2020-01-31 | 深圳顺络电子股份有限公司 | medium high Q microwave medium ceramic material and preparation method thereof |
| CN111138193A (en) * | 2020-01-03 | 2020-05-12 | 山东国瓷功能材料股份有限公司 | Microwave dielectric ceramic material with medium dielectric constant and preparation method and application thereof |
| CN111138193B (en) * | 2020-01-03 | 2022-03-01 | 山东国瓷功能材料股份有限公司 | Microwave dielectric ceramic material with medium dielectric constant and preparation method and application thereof |
| CN113105230A (en) * | 2021-03-18 | 2021-07-13 | 摩比天线技术（深圳）有限公司 | Microwave dielectric ceramic material for 5G base station and preparation method thereof |
| CN116969760A (en) * | 2023-08-01 | 2023-10-31 | 陕西华星电子开发有限公司 | Ca-Sm-Al-Ti-based microwave dielectric ceramic material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105000884A (en) | Microwave dielectric ceramic material as well as preparation method and application thereof | |
| CN104310980B (en) | A kind of microwave dielectric ceramic materials and preparation method thereof | |
| CN105399422A (en) | STLA microwave dielectric ceramic material and preparation method and application thereof | |
| CN106083033A (en) | A kind of microwave dielectric ceramic materials and preparation method thereof | |
| CN102584218B (en) | Environment-friendly microwave dielectric ceramic for L wave band | |
| WO2018177008A1 (en) | Environmentally-friendly microwave dielectric ceramic material for use in miniature navigation antenna | |
| CN103319166A (en) | Microwave ceramic medium material and preparation method thereof | |
| CN110066169B (en) | Silica-based low-dielectric-constant microwave dielectric ceramic and preparation method thereof | |
| CN110668795A (en) | Microwave dielectric ceramic material, preparation method and application thereof, microwave dielectric ceramic body, preparation method and application thereof, and microwave device | |
| CN103232235A (en) | Low-temperature sintered composite microwave dielectric ceramic material and preparation method thereof | |
| CN102603282A (en) | Ultralow-temperature sintering temperature stable-type microwave dielectric ceramic and preparation method thereof | |
| CN103113105B (en) | Low-temperature sintered high-dielectric-constant microwave dielectric ceramic and preparation method thereof | |
| CN101555135A (en) | Microwave medium ceramic material with ultrahigh Q-value middle dielectric constant | |
| CN113149645B (en) | Low-temperature sintering temperature stable composite microwave dielectric ceramic and preparation method thereof | |
| CN101913858B (en) | Li2O-ZnO-TiO2 microwave dielectric ceramic material and its preparation method | |
| CN105198423B (en) | Sr La Al base microwave medium ceramic materials and preparation method thereof | |
| CN103408299B (en) | Zinc barium titanate system ceramic low temperature sintering material and preparation method thereof | |
| CN102731092A (en) | Zr-Ti-based microwave dielectric ceramic material and preparation method thereof | |
| CN105130418A (en) | Li-Nb-Ti-based microwave dielectric ceramic material | |
| CN106587991B (en) | A kind of low temperature sintering composite microwave dielectric ceramic material and preparation method thereof | |
| CN105669195A (en) | Low-dielectric-constant and high-Q-value microwave dielectric ceramic material and preparation method thereof | |
| CN103408298B (en) | One is applicable to low sintering microwave dielectric ceramic materials and preparation method thereof | |
| CN114075070A (en) | Complex-phase microwave ceramic material, manufacturing method thereof and electronic device | |
| CN104193336A (en) | Low-sintering-temperature microwave dielectric ceramic material and preparation method thereof | |
| CN103159473A (en) | Microwave medium ceramic material and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151028 |