CN113998990A - Microwave dielectric ceramic material, microwave dielectric ceramic device and preparation method thereof - Google Patents
Microwave dielectric ceramic material, microwave dielectric ceramic device and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 44
- 239000000919 ceramic Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims abstract description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
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- 239000000843 powder Substances 0.000 claims description 54
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application discloses a microwave dielectric ceramic material, a microwave dielectric ceramic device and a preparation method thereof, and belongs to the technical field of communication. The microwave dielectric ceramic material comprises a ceramic main material and a modified additive accounting for 0-3 wt% of the ceramic main material; the composition expression of the ceramic main material is xAl2O3—（1‑x）TiO2And x is more than or equal to 0.86 and less than or equal to 0.94; the modifying additive comprises SiO2、Y2O3、MgO、Ga2O3ZnO and Nb2O5At least two of them. After the modification additive is added, the microwave dielectric ceramic material obtained by 1400 ℃ sintering and 1120 ℃ annealing treatment meets the requirements that the dielectric constant is near 11.0 and is continuously adjustable, and has extremely high Q f value and near-zero adjustable resonant frequency temperature coefficient.
Description
Technical Field
The embodiment of the application relates to the technical field of communication, in particular to a microwave dielectric ceramic material, a microwave dielectric ceramic device and a preparation method thereof.
Background
The rapid development of communication technology has gradually expanded communication technology from millimeter waves to millimeter waves. With the improvement of radio frequency, the delay phenomenon of signals in the transmission process becomes more and more serious, the loss of communication equipment is large, and the poor stability becomes a difficult problem in the industry. The microwave dielectric ceramic material is a key medium applied to microwave components such as a filter, a resonator, a substrate material, a dielectric waveguide loop and the like in a microwave frequency band (300MHz-30 GHz). In sub-millimeter and millimeter wave bands, the ceramic material with low dielectric constant can effectively reduce the coupling loss between the material and the electrode, thereby improving the propagation efficiency of signals. At present, microwave dielectric ceramics can be divided into three main categories, namely low dielectric constant (epsilon r is less than or equal to 20), medium dielectric constant (epsilon r is 20-40) and high dielectric constant (epsilon r is 70-100). The microwave ceramic material with low dielectric constant is widely applied to high-end microwave devices such as GPS (Global Positioning System) antennas, navigation, radars, satellite communication and the like, and can meet the requirements of microwave circuit miniaturization, integration, high reliability and low cost.
At present, the microwave dielectric ceramic material system with low dielectric constant mainly comprises a Mg-Si/Mg-Al-Si/Mg-Al-Si-Ti system, a Mg-Al-Nb system, an Al-Ti system and the like. These materials have a problem that the temperature coefficient of the resonance frequency is a large negative value.
Disclosure of Invention
The embodiment of the application provides a microwave dielectric ceramic material, a microwave dielectric ceramic device and a preparation method thereof, which are used for solving the problem that a microwave dielectric ceramic material system with a low dielectric constant has a larger negative value of a resonance frequency temperature coefficient. The technical scheme is as follows:
on one hand, the microwave dielectric ceramic material comprises a ceramic main material and a modified additive accounting for 0-3 wt% of the ceramic main material;
the composition expression of the ceramic main material is xAl2O3—(1-x)TiO2And x is more than or equal to 0.86 and less than or equal to 0.94;
the modifying additive comprises SiO2、Y2O3、MgO、Ga2O3ZnO and Nb2O5At least two of them.
In one aspect, there is provided a method for preparing a microwave dielectric ceramic material, for preparing the microwave dielectric ceramic material as claimed in claim 1, the method comprising:
according to xAl2O3—(1-x)TiO2Weighing Al according to stoichiometric ratio of expression2O3Powder, TiO2Adding pure water, a dispersing agent and a surfactant into the powder to perform primary ball milling to obtain a primary ball-milled raw material;
drying the raw materials subjected to the primary ball milling to obtain dried powder;
calcining the dried powder to obtain calcined powder;
mixing a selected amount of calcined powder and the modified additive to obtain a second mixture, adding water, a dispersant and a surfactant, performing secondary ball milling, mixing and dispersing, and performing sanding and redispersing treatment;
and adding glue into the sanded material, performing spray granulation, sieving the granulated powder with a 120-mesh sieve and a 250-mesh sieve, and taking the powder between the two sieves to obtain the microwave dielectric ceramic material.
In a possible implementation manner, the unit is expressed as xAl2O3—(1-x)TiO2Weighing Al according to stoichiometric ratio of expression2O3Powder, TiO2Adding pure water, a dispersing agent and a surfactant into the powder to perform primary ball milling to obtain a primary ball-milled raw material, wherein the primary ball-milled raw material comprises the following components:
according to xAl2O3—(1-x)TiO2Weighing the Al according to the stoichiometric ratio of the expression2O3Powder and the TiO2Pulverizing to obtain a first mixture;
adding water according to the mass ratio of the first mixture to the water of 1:1-1.8 for mixing;
and adding a dispersing agent and a surfactant which account for 0.4-1.5 wt% of the first mixture for primary ball milling to obtain a primary ball milled raw material.
In one possible implementation, the temperature of the calcination is 1150 ℃ to 1200 ℃, and the time of the calcination is 3 hours to 5 hours.
In a possible implementation manner, the calcining the dried powder to obtain a calcined powder includes:
and pouring the dried powder into a crucible and then calcining to obtain calcined powder.
In one possible implementation, the modifying additive includes SiO2、Y2O3、MgO、Ga2O3ZnO and Nb2O5At least two of; mixing a selected amount of calcined powder and the modified additive to obtain a second mixture, adding water, a dispersant and a surfactant, and performing secondary ball milling, mixing and dispersing, wherein the mixing and dispersing process comprises the following steps:
according to the mass ratio of the second mixture to water being 1: adding water in the proportion of 0.4-0.6 for mixing;
and adding a dispersing agent and a surfactant which account for 0.2-1.0 wt% of the second mixture for secondary ball milling and mixing dispersion.
In one possible implementation, the glue includes polyvinyl alcohol and PEG400, adding the sanded material into the glue and performing spray granulation, including:
and adding the sanded material into the glue, and adding a release agent and a defoaming agent to perform spray granulation, wherein the total glue content in the glue is 3-10 wt%.
In one aspect, a microwave dielectric ceramic device is provided, wherein the microwave dielectric ceramic device is prepared from the microwave dielectric ceramic material according to claim 1, and the microwave dielectric ceramic material is prepared by the preparation method according to any one of claims 2 to 7.
In one aspect, there is provided a method of manufacturing a microwave dielectric ceramic device, for manufacturing the microwave dielectric ceramic device as claimed in claim 8, the method comprising:
carrying out compression molding on the microwave dielectric ceramic material to obtain a blank body;
and carrying out heat preservation sintering on the blank at 1350-1400 ℃, and annealing at 1120 ℃.
The technical scheme provided by the embodiment of the application has the beneficial effects that at least:
through doping of the modified additive and annealing treatment at 1120 ℃, the temperature coefficient of the resonant frequency can be adjusted to be close to zero and a high quality factor can be kept, the sintering temperature of the microwave dielectric ceramic material is reduced from 1600 ℃ to 1400 ℃, and the microwave performance can meet the use requirement of the filter.
The microwave dielectric ceramic material has a high quality factor, a dielectric constant of 9.8-12.1, Q f at 25 ℃ of not less than 122000, and a resonance frequency Tf value close to zero, and can meet the use requirement of a filter; and the sintering temperature of the microwave dielectric ceramic material is 1380-1420 ℃, the low-temperature sintering performance is greatly improved, and the microwave dielectric ceramic material can be stably produced in batches.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of the preparation of microwave dielectric ceramic material;
FIG. 2 is an SEM topography of the microwave dielectric ceramic granulated powder prepared in example 7;
FIG. 3 is a graph showing the variation of the temperature coefficient Tf of the resonant frequency with the annealing time at different annealing temperatures of the microwave dielectric ceramic material prepared in example 7;
FIG. 4 is a graph showing the variation of the quality factor Qf with the annealing time at different annealing temperatures for the microwave dielectric ceramic material prepared in example 7.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present application more clear, the embodiments of the present application will be further described in detail with reference to the accompanying drawings.
The embodiment provides a microwave dielectric ceramic material, which comprises a ceramic main material and a modified additive accounting for 0-3 wt% of the ceramic main material; wherein the composition expression of the ceramic main material is xAl2O3—(1-x)TiO2And x is more than or equal to 0.86 and less than or equal to 0.94; the modifying additive comprises SiO2、Y2O3、MgO、Ga2O3ZnO and Nb2O5At least two of them.
The following is a description of the preparation method of the microwave dielectric ceramic material, and please refer to the flowchart illustrated in fig. 1.
S1, according to xAl2O3—(1-x)TiO2Weighing Al according to stoichiometric ratio of expression2O3Powder, TiO2And adding pure water, a dispersing agent and a surfactant into the powder to perform primary ball milling to obtain a primary ball milled raw material.
In particular, according to xAl2O3—(1-x)TiO2Weighing Al according to stoichiometric ratio of expression2O3Powder, TiO2Adding pure water, a dispersant and a surfactant into the powder to perform primary ball milling to obtain a primary ball-milled raw material, wherein the primary ball-milled raw material can comprise: according to xAl2O3—(1-x)TiO2Weighing Al according to stoichiometric ratio of expression2O3Powder and TiO2Pulverizing to obtain a first mixture; adding water according to the mass ratio of the first mixture to the water of 1:1-1.8 for mixing; and adding a dispersing agent and a surfactant which account for 0.4-1.5 wt% of the first mixture for primary ball milling to obtain a primary ball milled raw material.
S2, drying the raw materials subjected to the primary ball milling to obtain dried powder.
And S3, calcining the dried powder to obtain calcined powder.
Specifically, calcining the dried powder to obtain calcined powder may include: and pouring the dried powder into a crucible and then calcining to obtain calcined powder.
Wherein the calcining temperature is 1150-1200 ℃, and the calcining time is 3-5 hours.
And S4, mixing a selected amount of calcined powder with a modification additive to obtain a second mixture, adding water, a dispersant and a surfactant, performing secondary ball milling, mixing and dispersing, and performing sanding and redispersion treatment.
The modifying additive comprises SiO2、Y2O3、MgO、Ga2O3ZnO and Nb2O5Mixing the calcined powder and the modified additive to obtain a second mixture, adding water, a dispersant and a surfactant to perform secondary ball milling and mixing dispersion, wherein the mixing dispersion can comprise: according to the mass ratio of the second mixture to water of 1: adding water in the proportion of 0.4-0.6 for mixing; adding a dispersant and a surfactant which account for 0.2-1.0 wt% of the second mixture for secondary ball milling and mixing dispersion.
And S5, adding glue into the sanded material, performing spray granulation, sieving the granulated powder with a 120-mesh sieve and a 250-mesh sieve, and taking the powder between the two sieves to obtain the microwave dielectric ceramic material.
Specifically, glue includes polyvinyl alcohol and PEG400, adds glue and carries out the spray granulation with the material after the sanding, can include: and adding the sanded material into glue, adding a release agent and a defoaming agent, and performing spray granulation, wherein the total glue content in the glue is 3-10 wt%.
The following describes the preparation process by way of example. According to xAl2O3—(1-x)TiO2The stoichiometric ratio of the expression is respectively taken as Al2O3Powder, TiO2Mixing the powder to obtain a first mixture, and mixing the powder according to the first mixture: the mass ratio of water is 1: 1.2, adding water for mixing, adding a dispersing agent accounting for 0.5 wt% of the total weight of the first mixture and a surfactant accounting for 0.5 wt% of the total weight of the first mixture, performing first ball milling treatment by using agate balls, performing primary mixing and dispersion on the materials after ball milling for 4-6h, then placing the materials in a sand mill, further dispersing the materials by using zirconium balls with the diameter of 0.65mm as grinding media, drying the materials by using a microwave dryer after grinding until the water content is less than 1%, and calcining the dried materials by using a push plate furnace after sieving the materials by using a pulverizerThe calcination temperature is 1180 ℃, the heat preservation time is 3 hours, and the calcined material is placed for standby.
Taking the prepared xAl2O3—(1-x)TiO2100g of the material, and blending according to the components and the dosage of the auxiliary agent (additive or sintering auxiliary agent) shown in the following table 1 to obtain a second mixture, wherein the second mixture is prepared according to the following formula: mixing water according to the mass ratio of 1:0.5, adding a dispersing agent accounting for 0.6 wt% of the total amount of the second mixture and a surfactant accounting for 0.4%, performing secondary ball milling for 4-6h, primarily mixing and dispersing the materials, then placing the materials in a sand mill, and further dispersing the materials by using zirconium balls with the diameter of 1.5mm as grinding media.
Dissolving polyvinyl alcohol in water at 90 + -5 deg.C to obtain 10 wt% polyvinyl alcohol solution for use. Adding 3.0 wt% of polyvinyl alcohol glue solution, 1.5 wt% of PEG400 glue solution, 1.2 wt% of defoaming agent and 1.5 wt% of release agent which account for the solid mass of the raw materials into the obtained sanded chatty, and uniformly stirring; and spray-drying and granulating by a spray dryer, controlling the inlet temperature to be 220 +/-5 ℃ and the outlet temperature to be 120 +/-5 ℃, sieving by 60 meshes and 250 meshes, and taking the mixture to obtain the required composite microwave medium ceramic powder material. Wherein, the PEG400 glue is directly purchased liquid glue.
Table 1 shows the components and dosage of microwave dielectric ceramic material
And (3) respectively molding and sintering the granulated powder material, recording the sintering temperature of each green body, keeping the temperature for 4 hours, and respectively carrying out performance test on the microwave dielectric ceramic materials prepared in the embodiments 1-10.
The detection method in this embodiment is as follows:
1. the diameter and thickness of the sample are measured using a vernier caliper or micrometer.
2. The dielectric constant and Q f value at 25 ℃ of the obtained ceramic cylinder were measured by an Agilent E5071C network analyzer using a dielectric resonator complex dielectric constant measuring apparatus, and the resonance frequency temperature coefficient τ f was measured using a high/low temperature operating box.
The temperature coefficient of frequency τ f represents a good temperature characteristic, and is calculated by testing the resonance frequency f at-40 deg.C, 25 deg.C, and 130 deg.C, respectively, according to the following formula:
[(f110℃-f-40℃)/f-40℃*150]/(ppm/℃)。
the results of the measurements and calculations are shown in Table 2 below.
Table 2 shows the performance test results of the microwave dielectric ceramic material
Therefore, the microwave dielectric ceramic material prepared by the embodiment has a high quality factor, a dielectric constant of 9.89-11.31, a Q f at 25 ℃ of 120000, and a resonance frequency Tf value close to zero, and can meet the use requirement of a filter; and the sintering temperature of the microwave dielectric ceramic material is only 1400 ℃, the low-temperature sintering performance is greatly improved, and the microwave dielectric ceramic material can be stably produced in batches.
In this embodiment, the microwave dielectric ceramic material may be used to prepare a microwave dielectric ceramic device. Specifically, the microwave dielectric ceramic material can be pressed and formed to obtain a blank body; and (4) carrying out heat preservation sintering on the blank at 1350-1400 ℃, and annealing at 1120 ℃.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. The microwave dielectric ceramic material is characterized by comprising a ceramic main material and a modified additive accounting for 0-3 wt% of the ceramic main material;
the composition expression of the ceramic main material is xAl2O3—（1-x）TiO2And x is more than or equal to 0.86 and less than or equal to 0.94;
the modifying additive comprises SiO2、Y2O3、MgO、Ga2O3ZnO and Nb2O5At least two of them.
2. A method for preparing a microwave dielectric ceramic material, which is used for preparing the microwave dielectric ceramic material as claimed in claim 1, and comprises the following steps:
according to xAl2O3—（1-x）TiO2Weighing Al according to stoichiometric ratio of expression2O3Powder, TiO2Adding pure water, a dispersing agent and a surfactant into the powder to perform primary ball milling to obtain a primary ball-milled raw material;
drying the raw materials subjected to the primary ball milling to obtain dried powder;
calcining the dried powder to obtain calcined powder;
mixing a selected amount of calcined powder and the modified additive to obtain a second mixture, adding water, a dispersant and a surfactant, performing secondary ball milling, mixing and dispersing, and performing sanding and redispersing treatment;
and adding glue into the sanded material, performing spray granulation, sieving the granulated powder with a 120-mesh sieve and a 250-mesh sieve, and taking the powder between the two sieves to obtain the microwave dielectric ceramic material.
3. The method of claim 2, wherein the xAl is expressed as xAl2O3—（1-x）TiO2Weighing Al according to stoichiometric ratio of expression2O3Powder, TiO2Adding pure water, a dispersing agent and a surfactant into the powder to perform primary ball milling to obtain a primary ball-milled raw material, wherein the primary ball-milled raw material comprises the following components:
according to xAl2O3—（1-x）TiO2Weighing the Al according to the stoichiometric ratio of the expression2O3Powder and said TiO2Pulverizing to obtain a first mixture;
adding water according to the mass ratio of the first mixture to the water of 1:1-1.8 for mixing;
and adding a dispersing agent and a surfactant which account for 0.4-1.5 wt% of the first mixture for primary ball milling to obtain a primary ball milled raw material.
4. The method according to claim 2, wherein the temperature of the calcination is 1150 ℃ to 1200 ℃ and the time of the calcination is 3 hours to 5 hours.
5. The method of claim 2, wherein calcining the dried powder to obtain a calcined powder comprises:
and pouring the dried powder into a crucible and then calcining to obtain calcined powder.
6. The method of claim 2, wherein the modifying additive comprises SiO2、Y2O3、MgO、Ga2O3ZnO and Nb2O5At least two of; mixing a selected amount of calcined powder and the modified additive to obtain a second mixture, adding water, a dispersant and a surfactant, and performing secondary ball milling, mixing and dispersing, wherein the mixing and dispersing process comprises the following steps:
according to the mass ratio of the second mixture to water being 1: adding water in the proportion of 0.4-0.6 for mixing;
and adding a dispersing agent and a surfactant which account for 0.2-1.0 wt% of the second mixture for secondary ball milling and mixing dispersion.
7. The method of claim 2, wherein the glue comprises polyvinyl alcohol and PEG400, and the adding the sanded material to the glue and the spray granulating comprise:
and adding the sanded material into the glue, and adding a release agent and a defoaming agent to perform spray granulation, wherein the total glue content in the glue is 3-10 wt%.
8. A microwave dielectric ceramic device prepared from the microwave dielectric ceramic material according to claim 1, wherein the microwave dielectric ceramic material is prepared by the preparation method according to any one of claims 2 to 7.
9. A method for manufacturing a microwave dielectric ceramic device, for manufacturing a microwave dielectric ceramic device as claimed in claim 8, the method comprising:
carrying out compression molding on the microwave dielectric ceramic material to obtain a blank body;
and carrying out heat preservation sintering on the blank at 1350-1400 ℃, and annealing at 1120 ℃.
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