WO2012058916A1 - 微波介质谐振器及其制造方法和微波介质双工器 - Google Patents

微波介质谐振器及其制造方法和微波介质双工器 Download PDF

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WO2012058916A1
WO2012058916A1 PCT/CN2011/073991 CN2011073991W WO2012058916A1 WO 2012058916 A1 WO2012058916 A1 WO 2012058916A1 CN 2011073991 W CN2011073991 W CN 2011073991W WO 2012058916 A1 WO2012058916 A1 WO 2012058916A1
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microwave dielectric
mixed powder
dielectric resonator
ball
mixed
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PCT/CN2011/073991
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French (fr)
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肖培义
王瑾
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华为技术有限公司
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Priority to MX2011012653A priority Critical patent/MX2011012653A/es
Priority to BRPI1106087A priority patent/BRPI1106087A2/pt
Priority to CN201180001287.4A priority patent/CN102318135B/zh
Priority to HU1200482A priority patent/HUP1200482A2/hu
Publication of WO2012058916A1 publication Critical patent/WO2012058916A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint

Definitions

  • Microwave dielectric resonator, manufacturing method thereof and microwave dielectric duplexer The application is filed on November 1, 2010, the Chinese Patent Office, application number 201010532141.X, the invention name is "microwave dielectric resonator and its manufacturing method and microwave The priority of the Chinese Patent Application for the Medium Duplexer is hereby incorporated by reference in its entirety.
  • Embodiments of the present invention relate to the field of microwave media technologies, and in particular, to a microwave dielectric resonator, a manufacturing method thereof, and a microwave dielectric duplexer. Background technique
  • the microwave dielectric resonator has significant advantages such as high quality factor (Q: high value) and good frequency stability.
  • the microwave dielectric resonator generally includes a Transverse Electric and Magnetic Field (TEM) mode, a Transverse Magnetic Field (TM) mode, and a Transverse Electric Field (TE) mode.
  • TEM mode microwave dielectric resonators have been widely used in various communication terminals including mobile phones, mobile phones, walkie-talkies and the like. Since the communication base station has higher requirements on the Q value of the microwave medium, for example, the Q value is required to be greater than 6500 and the resonance frequency is 1908 MHz, but the TM mode microwave dielectric resonator cannot meet the requirements of the communication base station application due to limitations of materials and manufacturing processes. .
  • the technical composition of the microwave dielectric resonator mainly includes the formulation of the microwave ceramic material, the material and the dielectric resonator fabrication process.
  • a microwave dielectric material having a dielectric constant of "21" is taken as an example, and mainly includes a microwave dielectric material of a Ba-Mg-Ta system and a Ba-Mn-Ta system, but The price of Ta is too high, and the batch application is limited.
  • the microwave dielectric material of the Mg-Ca-Ti system is mainly used.
  • the micro-addition system of the microwave dielectric material is ZnO or SiO 2 or the like, or a trace amount of the sintering aid is rarely added.
  • Existing TM mode microwave dielectric material Q Value performance is generally between 3000 and 5000.
  • the ball mill mostly adopts the ordinary ball mill dispersion method, and adopts a single grinding ball with a larger particle diameter such as 6.5 mm or more; there are different degrees of residual carbon in the sintering process, such as: 0.5 % ⁇ 2% carbon residue.
  • the added micro-addition system of the existing microwave dielectric resonator mainly includes a cooling glass material such as ZnO and Si0 2 , the Q value performance and the frequency stability of the microwave dielectric resonator are low; if the ZnO or SiO 2 is reduced in order to improve the Q value performance When the amount is added, the sintering is difficult and the sintering density is poor. Summary of the invention
  • the invention provides a microwave dielectric resonator, a manufacturing method thereof and a microwave dielectric duplexer, which are used for solving the low-order Q performance and frequency stability of the microwave dielectric resonator in the prior art, and the sintering process is difficult, sintering
  • the denseness defect is low, the Q value performance and frequency stability of the microwave dielectric resonator are improved, the sintering temperature is lowered, and the sintering compactness is improved.
  • Embodiments of the present invention provide a method for fabricating a microwave dielectric resonator, including:
  • the main material is mixed by ball milling or sanding according to a set ratio to obtain a first mixed powder, and the main material includes Mg(OH) 2 , CaCO 3 and Ti0 2 ;
  • micro-additives in a set ratio to a ball mill to obtain a second mixed powder, the micro-additives including Zr0 2 , Nb 2 0 5 and Y 2 0 3 ;
  • the third mixed powder is subjected to die casting and sintering to obtain a microwave dielectric resonator.
  • the embodiment of the present invention further provides a microwave dielectric resonator prepared by the method for fabricating a microwave dielectric resonator according to any one of the embodiments of the present invention.
  • the embodiment of the present invention further provides a microwave dielectric duplexer, including: any microwave dielectric resonator provided by the embodiment of the present invention.
  • FIG. 1 is a flowchart of a method for fabricating a microwave dielectric resonator according to Embodiment 1 of the present invention
  • FIG. 2 is a flowchart of a method for fabricating a microwave dielectric resonator according to Embodiment 2 of the present invention
  • FIG. 4 is a flowchart of a method for fabricating a microwave dielectric resonator according to Embodiment 4 of the present invention
  • FIG. 5 is a manufacturing method of a microwave dielectric resonator according to Embodiment 5 of the present invention; Flow chart of the method. detailed description
  • the method for manufacturing the microwave dielectric resonator includes the following steps: Step 101: mixing the main material in a set ratio by ball milling or sanding to obtain a first mixed powder, wherein the main material comprises Mg(OH) 2 , CaCO 3 and Ti 0 2 ; therefore, the microwave dielectric resonance in the embodiment of the invention
  • the main formulation system of the apparatus is Mg (OH:> 2 -CaCO 3 -Ti0 2 system
  • the sintered ceramic system is MgO-CaO-Ti0 2 system or Mg-Ca-Ti system.
  • Mg in the embodiment of the present invention (OH) 2 , CaC0 3 and Ti0 2 may be selected from powders in form.
  • Step 102 mixing a trace amount of the additive into a ball mill according to a set ratio, to obtain a second mixed powder, wherein the trace additive comprises Zr0 2 , NbO and Yi 2 0 5 ; therefore, a trace amount of the microwave dielectric resonator in the embodiment of the invention
  • the addition system is a Zr0 2 -NbO-Yi 2 0 5 system, and Zr0 2 , NbO and Yi 2 0 5 in the embodiment of the present invention may be selected from powders.
  • the material may further include a minute amount of Zr0 2, Nb 2 0 5 and Y 2 0 3;
  • the system may also be added as Zr0 2 -Nb 2 0 5 -Y 2 In the 0 3 system, Zr0 2 , Nb 2 0 5 and Y 2 0 3 in the embodiment of the present invention may be selected from powders.
  • Step 103 mixing the first mixed powder and the second mixed powder by ball milling or sanding, and then granulating to obtain a third mixed powder;
  • Step 104 The third mixed powder is subjected to die casting and sintering to obtain a microwave dielectric resonator.
  • the main material for fabricating the microwave dielectric resonator of this embodiment includes Mg(OH) 2 , Ti0 2
  • the trace additive includes Zr0 2 , NbO and Yi 2 0 5
  • the trace additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3 , which can lower the sintering temperature, improve the compactness of the sintering, and inhibit the individual Excessive grain growth, control of compactness and grain uniformity, improve Q-value performance and frequency stability of microwave dielectric resonators;
  • micro-additives do not contain cooling glass materials, of which micro-additives may not contain ZnO, Si0 2 and other common cooling glass materials, further improve the Q value performance and frequency stability of microwave dielectric resonators.
  • step 101 of the method for manufacturing the microwave dielectric resonator specifically includes the following steps:
  • Step 201 Add a main material to the ball mill tank according to a set ratio, where the main material includes
  • Mg(OH) 2 , CaCO 3 and Ti0 2 wherein the mass ratio of the Mg(OH) 2 is 30% to 45 %, the mass ratio of the CaC0 3 is 2% to 10%, and the mass ratio of the Ti0 2 is 45% to 65%;
  • Step 202 adding water to the ball mill tank to which the main material is added;
  • Step 203 mixing the main material and water in a ball mill tank for 2 to 10 hours, and then taking out and draining from the ball mill tank;
  • Step 204 sintering the taken powder at 1000 ⁇ 1300 degrees for 2 ⁇ 6 hours;
  • Step 205 adding the sintered powder and water to the ball mill tank and mixing the ball mill for another 2 to 10 hours, or adding the sintered powder to the sand mill for 5-20 times, and drying to obtain the first A mixed powder.
  • the main material of the microwave dielectric resonator of the present embodiment includes Mg(OH) 2 , CaCO 3 and Ti0 2
  • the trace additive includes Zr0 2 , NbO and Yi 2 0 5
  • the trace additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3
  • the sintering is easy and the compactness is good, and the Q value performance and frequency stability of the microwave dielectric resonator can be improved
  • the micro-additive material does not contain the cooling glass material, wherein the micro-additive material may not Contains ZnO, Si0 2 and other commonly used cooling glass materials to further improve the Q value performance and frequency stability of microwave dielectric resonators.
  • the step 102 of the method for manufacturing the microwave dielectric resonator specifically includes the following steps:
  • Step 301 adding a trace amount of the additive to the ball mill tank according to a set ratio, wherein the trace additive comprises Zr0 2 , NbO and Yi 2 0 5 ; wherein the mass ratio of the Zr0 2 is 0 to 2%; The mass ratio of Yi 2 0 5 is 0 to 2%; the mass ratio of the NbO is 0 to 2%; wherein the starting additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3 ; the mass ratio of the ⁇ 2 0 3 is 0 ⁇ 2%; the mass ratio of the Nb 2 0 5 is 0 ⁇ 2%;
  • the micro-additive may further include: A1 2 0 3 and Si0 2 , the ratio of the A1 2 0 3 is 0 to 2%, and the ratio of the Si0 2 is 0 to 2%.
  • A1 2 0 3 and Si0 2 in the embodiment of the present invention The powder can be selected in form.
  • Step 302 adding water to the ball mill tank to which the trace additive is added;
  • Step 303 mixing the trace additive and water in a ball mill tank for 2 to 10 hours, and then taking out and draining from the ball mill tank;
  • Step 304 sintering the taken powder at 1000 ⁇ 1200 degrees for 2 ⁇ 5 hours;
  • Step 305 adding the sintered powder and water to the ball mill tank and mixing the ball mill for another 2 to 10 hours, and then drying to obtain the second mixed powder.
  • the main material of the microwave dielectric resonator of the present embodiment includes Mg(OH) 2 , CaCO 3 and Ti0 2
  • the trace additive includes Zr0 2 , NbO and Yi 2 0 5
  • the trace additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3 , can lower the sintering temperature, improve the compactness of sintering, suppress the excessive growth of individual crystal grains, control the compactness and grain uniformity, and improve the Q value and frequency stability of the microwave dielectric resonator.
  • the microwave dielectric resonator manufactured by the manufacturing method of the microwave dielectric resonator of the embodiment of the present invention has a dielectric constant of "21,", and the Q value of the specific single cavity test can reach more than 6500, which satisfies the communication base station to the micro-thin medium.
  • the trace additive does not contain the cooling glass material, wherein the trace additive can also contain no common cooling glass materials such as ZnO, Si0 2, etc., further improving the Q value performance and frequency stability of the microwave dielectric resonator;
  • the trace additive includes Zr0 2 , NbO and Yi 2 0 5 , wherein the trace additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3 even if a small amount of cooling glass is added.
  • the glass material Si0 2 has a very small effect on Q performance and frequency stability.
  • the step 103 of the method for manufacturing the microwave dielectric resonator specifically includes the following steps:
  • Step 401 adding the first mixed powder to a ball mill or a sand mill;
  • Step 402 adding water to a ball mill or a sand mill to which the first mixed powder is added, step 403, mixing the first mixed powder and water in a ball mill tank for 1 to 5 hours for the first time. , or sanding for 5 to 20 times in the sander for the first time; Step 404, adding the second mixed powder to the ball mill or sand mill after the first mixed ball mill;
  • Step 405 adding an organic dispersing agent to a ball mill or a sand mill to which the second mixed powder is added, wherein the content of the organic dispersing agent is 0.5% to 1% by mass;
  • Step 406 mixing the first ball-milled powder, the second mixed powder and the organic dispersing agent in a ball mill tank for a second time for 1 to 5 hours, or grinding the sanding machine for a second time 5 to 20
  • the organic dispersant may be selected, for example, such as ammonium polyamidoacrylate (PMAA-NH 4 ) or a material having similar dispersing properties.
  • Step 407 adding a polyvinyl alcohol (polyvinyl alcohol; PVA) solution having a concentration of 0.5% to the ball mill or sand mill after the second mixing ball milling;
  • PVA polyvinyl alcohol
  • Step 408 mixing the second mixed ball milled powder and the polyvinyl alcohol solution in a ball mill tank for 1 to 5 hours or sanding in a sand mill for 5-20 times, then spraying and granulating to obtain a third. Mix the powder.
  • the main material of the microwave dielectric resonator of the present embodiment includes Mg(OH) 2 , CaCO 3 and Ti0 2
  • the trace additive includes Zr0 2 , NbO and Yi 2 0 5
  • the trace additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3 , can lower the sintering temperature, improve the compactness of sintering, suppress the excessive growth of individual grains, control the compactness and grain uniformity, and improve the Q value performance and frequency stability of microwave dielectric resonators.
  • the micro-additives do not contain the cooling glass material.
  • the micro-additives may not contain the commonly used cooling glass materials such as ZnO and Si0 2 to further improve the Q value performance and frequency stability of the microwave dielectric resonator;
  • the additive includes Zr0 2 , NbO and Yi 2 0 5 , wherein the trace additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3 , even if a small amount of cooling glass material Si0 2 is added , the Q value performance and frequency are stable.
  • the effect of the effect is also very small; adding an organic dispersant before adding PVA can improve the powder dispersibility and reduce the phenomenon of powder agglomeration.
  • step 104 of the method for manufacturing the microwave dielectric resonator is shown in FIG. Specifically, the following steps are included:
  • Step 501 the third mixed powder is die-casted by using a pressure of 20 MPa to 200 MPa to obtain a green body;
  • Step 502 Sintering the green body under conditions of 1000 to 1400 degrees and passing moisture to obtain a microwave ceramic medium, wherein the temperature of the sintering is related to time: sintering at room temperature to 1000 degrees for 5 to 10 hours ; sintering at 1000 ⁇ 1400 degrees for 2 ⁇ 6 hours, the water temperature range of the moisture inlet water: 30 ⁇ 40 degrees;
  • Step 503 grinding, silvering, burning silver and testing the microwave ceramic medium to obtain the microwave dielectric resonator.
  • the main material of the microwave dielectric resonator of the present embodiment includes Mg(OH) 2 , CaCO 3 and Ti0 2
  • the trace additive includes Zr0 2 , NbO and Yi 2 0 5
  • the trace additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3 , can lower the sintering temperature, improve the compactness of sintering, suppress the excessive growth of individual grains, control the compactness and grain uniformity, and improve the Q value performance and frequency stability of microwave dielectric resonators.
  • the micro-additives do not contain the cooling glass material.
  • the micro-additives may not contain the commonly used cooling glass materials such as ZnO and Si0 2 to further improve the Q value performance and frequency stability of the microwave dielectric resonator;
  • the additive includes Zr0 2 , NbO and Yi 2 0 5 , wherein the trace additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3 , even if a small amount of cooling glass material Si0 2 is added , the Q value performance and frequency are stable.
  • the effect of the property is also very small; adding the organic dispersant before adding the PVA can improve the powder dispersibility and reduce the phenomenon of powder agglomeration; during the sintering process, the inlet air passes through the moisture during the sintering process Heating segment may facilitate negative organic material, reducing residual carbon after sintering, to further improve the Q value in microwave dielectric resonators.
  • one or more zirconia spheres or cylinders of different particle diameters may be used in combination, wherein the zirconia spheres or cylinders have a particle size ranging from 1.5 mm to 6.5 mm.
  • the zirconia spheres or cylinders have a particle size ranging from 1.5 mm to 6.5 mm.
  • two zirconia balls with a particle size of 1.5 mm, a particle size of 4 mm, and a particle size of 6.5 mm are used; or six particle sizes of 1.5 mm are used in a single mixing ball milling process.
  • Zirconium oxide sphere, another particle size of 4mm used in the mixing ball milling process Zirconia spheres.
  • a zirconia sphere with a particle size of 1.5 mm, a particle size of 4 mm, and a particle size of 6.5 mm is mixed in a single mixing ball milling process in a ratio of 2:1:1; or a single mixing ball milling process.
  • a zirconia sphere having a diameter of 1.5 mm is used, and a zirconia sphere having a particle diameter of 4 mm is used in the other mixing ball milling process.
  • the use of balls or cylinders of different particle sizes in the mixing ball milling process can improve the dispersion effect of the mixing ball mill and ensure the normal distribution of the powder particle size.
  • the parameters of the mixing ball mill and the grinding wheel speed can also be adjusted.
  • the microwave dielectric resonator provided in Embodiment 6 of the present invention can be manufactured by using any one of the microwave dielectric resonator manufacturing methods of the embodiments of the present invention.
  • the main material of the microwave dielectric resonator of the present embodiment includes Mg(OH) 2 , CaCO 3 and Ti0 2
  • the trace additive includes Zr0 2 , NbO and Yi 2 0 5
  • the trace additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3 , can lower the sintering temperature, improve the compactness of sintering, suppress the excessive growth of individual grains, control the compactness and grain uniformity, and improve the Q value performance and frequency stability of microwave dielectric resonators.
  • the micro-additives do not contain the cooling glass material.
  • the micro-additives may not contain the commonly used cooling glass materials such as ZnO and Si0 2 to further improve the Q value performance and frequency stability of the microwave dielectric resonator;
  • the additive includes Zr0 2 , NbO and Yi 2 0 5 , wherein the trace additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3 , even if a small amount of cooling glass material Si0 2 is added , the Q value performance and frequency are stable.
  • the sexual impact is also very small.
  • a seventh embodiment of the present invention provides a microwave dielectric duplexer, including: any of the microwave dielectric resonators provided by the embodiments of the present invention.
  • the microwave dielectric resonator is a core component of the microwave dielectric duplexer, and the duplexer of the communication base station can adopt the miniaturized, low power consumption microwave dielectric duplexer provided in the embodiment of the present invention.
  • the trace additive includes Zr0 2 , Nb 2 0 5 and Y 2 0 3 , wherein, micro
  • the amount of additive may also include Zr0 2 , Nb 2 0 5 and Y 2 0 3 , which can lower the sintering temperature, improve the compactness of the sintering, suppress the excessive growth of individual grains, control the compactness and grain uniformity, and improve the microwave medium.
  • the trace additive includes Zr0 2 , NbO and Yi 2 0 5 , wherein the trace additive may further include Zr0 2 , Nb 2 0 5 and Y 2 0 3 even if a small amount of cooling glass material is added.
  • Si0 2 has a very small effect on Q performance and frequency stability.

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Description

微波介质谐振器及其制造方法和微波介质双工器 本申请要求于 2010 年 11 月 01 日提交中国专利局、 申请号为 201010532141.X,发明名称为"微波介质谐振器及其制造方法和微波介质双工 器"的中国专利申请的优先权， 其全部内容通过引用结合在本申请中。 技术领域
本发明实施例涉及微波介质技术领域， 尤其涉及一种微波介质谐振器及 其制造方法和微波介质双工器。 背景技术
微波介质谐振器具有品质因素 （Quality; 简称： Q )值高、 频率稳定性 好等显著优点。微波介质谐振器一般包括：横向电磁场（ Transverse Electric and Magnetic Field; 简称： TEM )模式、 横向磁场（ Transverse Magnetic Field; 简称： TM )模式和横向电场 （Transverse Electric Field; 简称： TE )模式。 随着通讯行业的发展， TEM模式的微波介质谐振器在各种通讯终端包括手 机、 移动电话、 对讲机等方面得到广泛应用。 由于通讯基站对于微波介质的 Q值要求更高， 例如： 要求 Q值大于 6500,谐振频率达到 1908MHZ, 但 TM 模式的微波介质谐振器由于材料与制作工艺的限制， 一直无法达到通讯基站 应用的要求。
微波介质谐振器的技术构成主要包括微波陶瓷材料配方、 材料与介质谐 振器制作工艺。在 TM模式的微波介质谐振器的材料方面，以介电常数为 "21" 左右的微波介质材料为例， 主要包括 Ba-Mg-Ta体系、 Ba-Mn-Ta体系的微波 介质材料， 但由于 Ta的价格过高， 批量应用受限， 在手机终端方面， 主要使 用 Mg-Ca-Ti体系的微波介质材料。 另外， 微波介质材料的微量添加体系是 ZnO或 Si02等或极少添加微量助烧材料。 现有 TM模式的微波介质材料的 Q 值性能一般在 3000 ~ 5000之间。 在微波介质谐振器的工艺制造过程中， 球磨 多采用普通的球磨分散方式， 采用较大粒径如 6.5mm或以上的单一磨球； 在 烧结过程存在不同程度的残留碳现象如： 0.5 % ~ 2 %的碳残留现象。
由于现有微波介质谐振器的添加微量添加体系主要包括 ZnO、 Si02等降 温玻璃材料， 导致微波介质谐振器的 Q值性能和频率稳定性低； 如果为了提 高 Q值性能减少 ZnO或 Si02的添加量， 则导致烧结难度大， 烧结致密性差。 发明内容
本发明提供一种微波介质谐振器及其制造方法和微波介质双工器， 用以 解决现有技术中的微波介质谐振器的 Q值性能和频率稳定性低， 制造过程的 烧结难度大， 烧结致密性差缺陷， 提高微波介质谐振器的 Q值性能和频率稳 定性低， 降低烧结温度， 改善烧结致密性。
本发明实施例提供一种微波介质谐振器的制造方法， 包括：
将主材料按照设定比例混合球磨或砂磨， 得到第一混合粉体， 所述主材 料包括 Mg(OH)2、 CaC03和 Ti02;
将微量添加料按照设定比例混合球磨， 得到第二混合粉体， 所述微量添 加料包括 Zr02、 Nb205和 Y203；
将所述第一混合粉体与第二混合粉体混合球磨或砂磨后造粒， 得到第三 混合粉体；
将所述第三混合粉体经过压铸成型和烧结得到微波介质谐振器。
本发明实施例还提供一种根据本发明实施例提供的任一所述的微波介质 谐振器的制造方法制得的微波介质谐振器。
本发明实施例还提供一种微波介质双工器， 包括： 本发明实施例提供的 任意一种微波介质谐振器。
本发明提供的微波介质谐振器及其制造方法和微波介质双工器， 制造微 波介质谐振器的主材料包括 Mg(OH)2、 CaC03和 Ti02,微量添加料包括 Zr02、 NbO和 Yi205, 其中， 微量添加料还可以包括 Zr02、 Nb205和 Y203, 可以降 低烧结温度， 改善烧结致密性， 抑制个别晶粒的过分增长， 控制致密性与晶 粒的一致性， 提高微波介质谐振器的 Q值性能与频率稳定性； 微量添加料中 不含降温玻璃材料， 其中， 微量添加料中还可以不含 ZnO、 Si02等常用降温 玻璃材料， 进一步提高微波介质谐振器的 Q值性能与频率稳定性。 附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案， 下面将对实 施例或现有技术描述中所需要使用的附图作一简单地介绍， 显而易见地， 下 面描述中的附图是本发明的一些实施例， 对于本领域普通技术人员来讲， 在 不付出创造性劳动的前提下， 还可以根据这些附图获得其他的附图。
图 1为本发明实施例一提供的微波介质谐振器的制造方法的流程图； 图 2为本发明实施例二提供的微波介质谐振器的制造方法的流程图； 图 3为本发明实施例三提供的微波介质谐振器的制造方法的流程图； 图 4为本发明实施例四提供的微波介质谐振器的制造方法的流程图； 图 5为本发明实施例五提供的微波介质谐振器的制造方法的流程图。 具体实施方式
为使本发明实施例的目的、 技术方案和优点更加清楚， 下面将结合本发 明实施例中的附图， 对本发明实施例中的技术方案进行清楚、 完整地描述， 显然， 所描述的实施例是本发明一部分实施例， 而不是全部的实施例。 基于 本发明中的实施例， 本领域普通技术人员在没有作出创造性劳动前提下所获 得的所有其他实施例， 都属于本发明保护的范围。
实施例一
图 1为本发明实施例一提供的微波介质谐振器的制造方法的流程图， 如 图 1所示， 该微波介质谐振器的制造方法包括以下步骤： 步骤 101、 将主材料按照设定比例混合球磨或砂磨， 得到第一混合粉体， 所述主材料包括 Mg(OH)2、 CaC03和 Ti02; 因此， 本发明实施例中微波介质 谐振器的主要配方体系是 Mg(OH:>2-CaC03-Ti02体系， 烧结后的陶瓷体系是 MgO-CaO-Ti02体系或 Mg-Ca-Ti体系。 其中， 本发明实施例中的 Mg(OH)2、 CaC03和 Ti02在形态上可以选用粉体。
步骤 102、 将微量添加料按照设定比例混合球磨， 得到第二混合粉体， 所述 微量添加料包括 Zr02、 NbO和 Yi205; 因此， 本发明实施例中微波介质谐振器的 微量添加体系为 Zr02-NbO-Yi205体系， 本发明实施例中的 Zr02、 NbO和 Yi205 在形态上可以选用粉体。此外，所述微量添加料还可以包括 Zr02、 Nb205和 Y203; 本发明实施例中微波介质谐振器的微量添加体系还可以为为 Zr02-Nb205-Y203体 系， 本发明实施例中的 Zr02、 Nb205和 Y203在形态上可以选用粉体。
步骤 103、 将所述第一混合粉体与第二混合粉体混合球磨或砂磨后造粒， 得到第三混合粉体；
步骤 104、将所述第三混合粉体经过压铸成型和烧结得到微波介质谐振器。 本实施例制造微波介质谐振器的主材料包括 Mg(OH)2、
Figure imgf000006_0001
Ti02, 微 量添加料包括 Zr02、 NbO和 Yi205，其中，微量添加料还可以包括 Zr02、 Nb205 和 Y203, 可以降低烧结温度， 改善烧结致密性， 抑制个别晶粒的过分增长， 控 制致密性与晶粒的一致性， 提高微波介质谐振器的 Q值性能与频率稳定性； 微 量添加料中不含降温玻璃材料， 其中， 微量添加料中还可以不含 ZnO、 Si02等 常见降温玻璃材料， 进一步提高微波介质谐振器的 Q值性能与频率稳定性。
实施例二
图 2为本发明实施例二提供的微波介质谐振器的制造方法的流程图， 如 图 2所示， 上述实施例的基础上， 该微波介质谐振器的制造方法的步骤 101 具体包括以下步骤：
步骤 201、 将主材料按照设定比例添加到球磨罐中， 所述主材料包括
Mg(OH)2、 CaC03和 Ti02, 其中所述 Mg(OH)2所占的质量比例为 30 % ~ 45 % , 所述 CaC03所占的质量比例为 2 % ~ 10 % , 所述 Ti02所占的质量比例为 45 % ~ 65 %；
步骤 202、 向添加了所述主材料的球磨罐中添加水；
步骤 203、 将所述主材料和水在球磨罐中混合球磨 2 ~ 10小时后从球磨 罐中取出沥干；
步骤 204、 在 1000 ~ 1300度将取出的粉体烧结 2 ~ 6小时；
步骤 205、 将烧结后的粉体和水添加到球磨罐中再次混合球磨 2 ~ 10小 时， 或将烧结后的粉体加入砂磨机中砂磨 5 ~ 20次后， 烘干得到所述第一混 合粉体。
本实施例制造微波介质谐振器的主材料包括 Mg(OH)2、 CaC03和 Ti02, 微量添加料包括 Zr02、 NbO和 Yi205, 其中， 微量添加料还可以包括 Zr02、 Nb205和 Y203, 烧结容易且致密性好， 可以提高微波介质谐振器的 Q值性能 与频率稳定性； 微量添加料中不含降温玻璃材料， 其中， 微量添加料中还可 以不含 ZnO、 Si02等常用降温玻璃材料， 进一步提高微波介质谐振器的 Q值 性能与频率稳定性。
实施例三
图 3为本发明实施例三提供的微波介质谐振器的制造方法的流程图， 如 图 3所示， 上述实施例的基础上， 该微波介质谐振器的制造方法的步骤 102 具体包括以下步骤：
步骤 301、 将微量添加料按照设定比例添加到球磨罐中， 所述微量添加 料包括 Zr02、 NbO和 Yi205; 其中所述 Zr02所占的质量比例为 0 ~ 2 %； 所述 Yi205所占的质量比例为 0 ~ 2 %；所述 NbO所占的质量比例为 0 ~ 2 %；其中， 啟量添加料还可以包括 Zr02、 Nb205和 Y203； 所述 Υ203所占的质量比例为 0 ~ 2 %； 所述 Nb205所占的质量比例为 0 ~ 2 %；
其中， 微量添加料中还可以包括： A1203和 Si02, 所述 A1203所占的比例 为 0 ~ 2 % ,所述 Si02所占的比例为 0 ~ 2 %。本发明实施例中的 A1203和 Si02 在形态上可以选用粉体。
步骤 302、 向添加了所述微量添加料的球磨罐中添加水；
步骤 303、 将所述微量添加料和水在球磨罐中混合球磨 2 ~ 10小时后从 球磨罐中取出沥干；
步骤 304、 在 1000 ~ 1200度将取出的粉体烧结 2 ~ 5小时；
步骤 305、 将烧结后的粉体和水添加到球磨罐中再次混合球磨 2 ~ 10小 时后， 烘干得到第二混合粉体。
本实施例制造微波介质谐振器的主材料包括 Mg(OH)2、 CaC03和 Ti02, 微量添加料包括 Zr02、 NbO和 Yi205, 其中， 微量添加料还可以包括 Zr02、 Nb205和 Y203, 可以降低烧结温度， 改善烧结致密性， 抑制个别晶粒的过分 增长， 控制致密性与晶粒的一致性， 提高微波介质谐振器的 Q值与频率稳定 性， 例如： 采用本发明实施例微波介质谐振器的制造方法制造的介电常数为 "21，，左右的微波介质谐振器，在特定单腔测试 Q值性能可达到 6500以上， 满 足通讯基站对微薄介质谐振器的需求； 微量添加料中不含降温玻璃材料， 其 中， 微量添加料中还可以不含 ZnO、 Si02等常用降温玻璃材料， 进一步提高 微波介质谐振器的 Q值性能与频率稳定性；此外，由于微量添加料包括 Zr02、 NbO和 Yi205, 其中， 微量添加料还可以包括 Zr02、 Nb205和 Y203, 即使加 入少量降温玻璃材料 Si02, 对 Q值性能与频率稳定性影响也非常小。
实施例四
图 4为本发明实施例四提供的微波介质谐振器的制造方法的流程图， 如 图 4所示， 上述实施例的基础上， 该微波介质谐振器的制造方法的步骤 103 具体包括以下步骤：
步骤 401、 将所述第一混合粉体添加到球磨罐或砂磨机中；
步骤 402、 向添加了所述第一混合粉体的球磨罐或砂磨机中添加水， 步骤 403、 将所述第一混合粉体和水在球磨罐中第一次混合球磨 1 ~ 5小 时， 或在砂磨机中第一次砂磨 5 ~ 20次； 步骤 404、 向第一次混合球磨后的球磨罐或砂磨机中添加所述第二混合 粉体；
步骤 405、 向添加了所述第二混合粉体的球磨罐或砂磨机中添加有机分 散剂， 所述有机分散剂的含量所占的质量比例为 0.5 % ~ 1 %；
步骤 406、 将第一次混合球磨后的粉体、 第二混合粉体和有机分散剂在 球磨罐中第二次混合球磨 1 ~ 5小时，或在砂磨机第二次砂磨 5 ~ 20次；其中， 有机分散剂可以选择例如： 比如聚曱基丙烯酸铵 ( PMAA-NH4 )或与之分散 性能相似的材料。
步骤 407、 向第二次混合球磨后的所述球磨罐或砂磨机中添加浓度为 0.5 %的聚乙烯醇 （ polyvinyl alcohol; 简称： PVA )溶液；
步骤 408、 将第二次混合球磨后的粉体和所述聚乙烯醇溶液在球磨罐中 混合球磨 1 ~ 5小时或在砂磨机中砂磨 5 ~ 20次后喷雾造粒，得到第三混合粉 体。
本实施例制造微波介质谐振器的主材料包括 Mg(OH)2、 CaC03和 Ti02, 微量添加料包括 Zr02、 NbO和 Yi205, 其中， 微量添加料还可以包括 Zr02、 Nb205和 Y203, 可以降低烧结温度， 改善烧结致密性， 抑制个别晶粒的过分 增长， 控制致密性与晶粒的一致性， 提高微波介质谐振器的 Q值性能与频率 稳定性； 微量添加料中不含降温玻璃材料， 其中， 微量添加料中还可以不含 ZnO、 Si02等常用降温玻璃材料， 进一步提高微波介质谐振器的 Q值性能与 频率稳定性； 此外， 由于微量添加料包括 Zr02、 NbO和 Yi205, 其中， 微量 添加料还可以包括 Zr02、 Nb205和 Y203, 即使加入少量降温玻璃材料 Si02, 对 Q值性能与频率稳定性影响也非常小； 在添加 PVA前加入有机分散剂， 可以提高粉体分散性， 降低粉体团聚现象。
实施例五
图 5为本发明实施例五提供的微波介质谐振器的制造方法的流程图， 如 图 5所示， 上述实施例的基础上， 该微波介质谐振器的制造方法的步骤 104 具体包括以下步骤：
步骤 501、采用 20MPa〜200MPa的压力， 将所述第三混合粉体压铸成型， 得到坯体；
步骤 502、 在 1000 ~ 1400度且通入湿气的条件下， 烧结所述坯体得到微 波陶瓷介质， 其中， 所述烧结的温度与时间的关系为： 在室温 ~ 1000度烧结 5 ~ 10小时； 在 1000 ~ 1400度烧结 2 ~ 6小时， 所述湿气进气过水的水温范 围为： 30 ~ 40度；
步骤 503、 对所述微波陶瓷介质进行打磨、 披银、 烧银和测试， 得到所 述微波介质谐振器。
本实施例制造微波介质谐振器的主材料包括 Mg(OH)2、 CaC03和 Ti02, 微量添加料包括 Zr02、 NbO和 Yi205, 其中， 微量添加料还可以包括 Zr02、 Nb205和 Y203, 可以降低烧结温度， 改善烧结致密性， 抑制个别晶粒的过分 增长， 控制致密性与晶粒的一致性， 提高微波介质谐振器的 Q值性能与频率 稳定性； 微量添加料中不含降温玻璃材料， 其中， 微量添加料中还可以不含 ZnO、 Si02等常用降温玻璃材料， 进一步提高微波介质谐振器的 Q值性能与 频率稳定性； 此外， 由于微量添加料包括 Zr02、 NbO和 Yi205, 其中， 微量 添加料还可以包括 Zr02、 Nb205和 Y203, 即使加入少量降温玻璃材料 Si02, 对 Q值性能与频率稳定性影响也非常小； 在添加 PVA前加入有机分散剂， 可以提高粉体分散性， 降低粉体团聚现象； 烧结过程中， 烧结坯体的过程中 进气过水通入湿气， 可以促进升温段的有机物质排除， 减少烧结后的碳残留， 进一步提高微波介质谐振器的 Q值性能。
上述实施例中的所有混合球磨的过程中， 都可以将一个以上不同粒径的 氧化锆圆球或圆柱混合使用， 其中， 所述氧化锆圆球或圆柱粒径范围为 1.5mm〜6.5mm。 例如： 一次混合球磨过程中采用 2个粒径为 1.5mm、 1个粒 径为 4mm、一个粒径为 6.5mm的氧化锆圆球； 或者一次混合球磨过程中采用 6个粒径为 1.5mm的氧化锆圆球，另一次混合球磨过程中采用 2个粒径为 4mm 的氧化锆圆球。再如： 一次混合球磨过程中采用粒径为 1.5mm、粒径为 4mm、 粒径为 6.5mm的氧化锆圆球按照数量比 2: 1 : 1来混合； 或者一次混合球磨 过程中全部采用粒径为 1.5mm的氧化锆圆球， 另一次混合球磨过程中采用粒 径为 4mm的氧化锆圆球。本发明实施例混合球磨过程中搭配使用不同粒径圆 球或圆柱， 可以提高混合球磨的分散效果， 确保粉体粒度的正态分布。 为了 进一步优化混合球磨的分散效果， 确保粉体粒度的正态分布， 还可以调整混 合球磨的时间和磨球转速等参数。
实施例六
本发明实施例六提供的微波介质谐振器可以采用本发明实施例中的任意 一种微波介质谐振器的制造方法制得。
本实施例制造微波介质谐振器的主材料包括 Mg(OH)2、 CaC03和 Ti02, 微量添加料包括 Zr02、 NbO和 Yi205, 其中， 微量添加料还可以包括 Zr02、 Nb205和 Y203, 可以降低烧结温度， 改善烧结致密性， 抑制个别晶粒的过分 增长， 控制致密性与晶粒的一致性， 提高微波介质谐振器的 Q值性能与频率 稳定性； 微量添加料中不含降温玻璃材料， 其中， 微量添加料中还可以不含 ZnO、 Si02等常用降温玻璃材料， 进一步提高微波介质谐振器的 Q值性能与 频率稳定性； 此外， 由于微量添加料包括 Zr02、 NbO和 Yi205, 其中， 微量 添加料还可以包括 Zr02、 Nb205和 Y203, 即使加入少量降温玻璃材料 Si02, 对 Q值性能与频率稳定性影响也非常小。
实施例七
本发明实施例七提供一种微波介质双工器， 包括： 本发明实施例提供的 任意一种微波介质谐振器。 微波介质谐振器是微波介质双工器的核心部件， 通讯基站的双工器可以采用本发明实施例中提供的小型化、 低功耗的微波介 质双工器。
本实施例微波介质双工器的微波介质谐振器制造所采用的主材料包括
Mg(OH)2、 CaC03和 Ti02, 微量添加料包括 Zr02、 Nb205和 Y203, 其中， 微 量添加料还可以包括 Zr02、 Nb205和 Y203, 可以降低烧结温度， 改善烧结 致密性， 抑制个别晶粒的过分增长， 控制致密性与晶粒的一致性， 提高微波 介质谐振器的 Q值性能与频率稳定性； 微量添加料中不含降温玻璃材料， 其 中， 微量添加料中还可以不含 ZnO、 Si02等常用降温玻璃材料， 进一步提高 微波介质谐振器的 Q值性能与频率稳定性；此外，由于微量添加料包括 Zr02、 NbO和 Yi205, 其中， 微量添加料还可以包括 Zr02、 Nb205和 Y203, 即使加 入少量降温玻璃材料 Si02, 对 Q值性能与频率稳定性影响也非常小。
最后应说明的是： 以上实施例仅用以说明本发明的技术方案， 而非对其 限制； 尽管参照前述实施例对本发明进行了详细的说明， 本领域的普通技术 人员应当理解： 其依然可以对前述各实施例所记载的技术方案进行修改， 或 者对其中部分技术特征进行等同替换； 而这些修改或者替换， 并不使相应技 术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims

权 利 要 求
1、 一种微波介质谐振器的制造方法， 其特征在于， 包括：
将主材料按照设定比例混合球磨或砂磨， 得到第一混合粉体， 所述主材 料包括 Mg(OH)2、 CaC03和 Ti02;
将微量添加料按照设定比例混合球磨， 得到第二混合粉体， 所述微量添 加料包括 Zr02、 Nb205和 Y203；
将所述第一混合粉体与第二混合粉体混合球磨或砂磨后造粒， 得到第三 混合粉体；
将所述第三混合粉体经过压铸成型和烧结得到微波介质谐振器。
2、 根据权利要求 1所述的微波介质谐振器的制造方法， 其特征在于， 所 述将主材料按照设定比例混合球磨或砂磨， 得到第一混合粉体， 所述主材料 包括 Mg(OH)2、 CaC03 ^ Ti02, 具体为：
将主材料按照设定比例添加到球磨罐中， 所述主材料包括 Mg(OH)2、 CaC03和 Ti02 ,其中所述 Mg(OH)2所占的质量比例为 30 % ~ 45 % ,所述 CaC03 所占的质量比例为 2 % ~ 10 % , 所述 Ti02所占的质量比例为 45 % - 65 %； 向添加了所述主材料的球磨罐中添加水；
将所述主材料和水在球磨罐中混合球磨 2 ~ 10小时后从球磨罐中取出沥 干；
在 1000 ~ 1300度将取出的粉体烧结 2 ~ 6小时；
将烧结后的粉体和水添加到球磨罐中再次混合球磨 2 ~ 10小时， 或将烧 结后的粉体加入砂磨机中砂磨 5 ~ 20次后， 烘干得到所述第一混合粉体。
3、 根据权利要求 2所述的微波介质谐振器的制造方法， 其特征在于， 所 述将微量添加料按照设定比例混合球磨， 得到第二混合粉体， 所述微量添加 料包括 Zr02、 Nb205和 Y203, 具体为：
将微量添加料按照设定比例添加到球磨罐中 ,所述微量添加料包括 Zr02、
Nb205和 Y203; 其中所述 Zr02所占的质量比例为 0 ~ 2 %； 所述 Y203所占的 质量比例为 0 ~ 2 %； 所述 Nb205所占的质量比例为 0 ~ 2 %；
向添加了所述微量添加料的球磨罐中添加水；
将所述微量添加料和水在球磨罐中混合球磨 2 ~ 10小时后从球磨罐中取 出沥干；
在 1000 ~ 1200度将取出的粉体烧结 2 ~ 5小时；
将烧结后的粉体和水添加到球磨罐中再次混合球磨 2 ~ 10小时后， 烘干 得到第二混合粉体。
4、 根据权利要求 3所述的微波介质谐振器的制造方法， 其特征在于， 所 述啟量添加料还包括： A1203和 Si02 , 所述 A1203所占的比例为 0 ~ 2 % , 所述 Si02所占的比例为 0 ~ 2 %。
5、 根据权利要求 2、 3或 4所述的微波介质谐振器的制造方法， 其特征 在于， 将所述第一混合粉体与第二混合粉体混合球磨或砂磨后造粒， 得到第 三混合粉体， 具体为：
将所述第一混合粉体添加到球磨罐或砂磨机中；
向添加了所述第一混合粉体的球磨罐或砂磨机中添加水；
将所述第一混合粉体和水在球磨罐中第一次混合球磨 1 ~ 5小时，或在砂 磨机中第一次砂磨 5 ~ 20次；
向第一次混合球磨后的球磨罐或砂磨机中添加所述第二混合粉体； 向添加了所述第二混合粉体的球磨罐或砂磨机中添加有机分散剂， 所述 有机分散剂的含量所占的质量比例为 0.5 % ~ 1 %；
将第一次混合球磨后的粉体、 第二混合粉体和有机分散剂在球磨罐中第 二次混合球磨 1 ~ 5小时， 或在砂磨机第二次砂磨 5 ~ 20次；
向第二次混合球磨后的所述球磨罐或砂磨机中添加浓度为 0.5 %的聚乙 烯醇溶液；
将第二次混合球磨后的粉体和所述聚乙烯醇溶液在球磨罐中混合球磨
1 ~ 5小时或在砂磨机中砂磨 5 ~ 20次后喷雾造粒， 得到第三混合粉体。
6、 根据权利要求 5所述的微波介质谐振器的制造方法， 其特征在于， 所 述有机分散剂为聚曱基丙烯酸铵。
7、 根据权利要求 1所述的微波介质谐振器的制造方法， 其特征在于， 所 述将所述第三混合粉体经过压铸成型和烧结得到微波介质谐振器， 具体为： 采用 20MPa〜200MPa的压力，将所述第三混合粉体压铸成型，得到坯体； 在 1000 ~ 1400度且通入湿气的条件下， 烧结所述坯体得到微波陶瓷介 质， 其中， 所述烧结的温度与时间的关系为： 在室温 ~ 1000度烧结 5 ~ 10小 时；在 1000 ~ 1400度烧结 2 ~ 6小时，所述湿气进气过水的水温范围为： 30 ~ 40度；
对所述微波陶瓷介质进行打磨、 披银、 烧银和测试， 得到所述微波介质 谐振器。
8、 根据权利要求 1-4任一所述的微波介质谐振器的制造方法， 其特征在 于： 在所述混合球磨过程中， 将一个以上不同粒径的氧化锆圆球或圆柱混合 使用， 所述氧化锆圆球或圆柱粒径范围为 1.5mm〜6.5mm。
9、 一种根据权利要求 1-8任一所述的微波介质谐振器的制造方法制得的 微波介质谐振器。
10、 一种微波介质双工器， 其特征在于， 包括： 权利要求 9所述的微波 介质谐振器。
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