WO2017113218A1 - Ceramic materials and preparation method therefor, resonator, filter and radio frequency remote device - Google Patents

Ceramic materials and preparation method therefor, resonator, filter and radio frequency remote device Download PDF

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Publication number
WO2017113218A1
WO2017113218A1 PCT/CN2015/099947 CN2015099947W WO2017113218A1 WO 2017113218 A1 WO2017113218 A1 WO 2017113218A1 CN 2015099947 W CN2015099947 W CN 2015099947W WO 2017113218 A1 WO2017113218 A1 WO 2017113218A1
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preparation
resonator
dielectric ceramic
ceramic material
organic binder
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PCT/CN2015/099947
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French (fr)
Chinese (zh)
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庄后荣
陆正武
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深圳市大富科技股份有限公司
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Priority to PCT/CN2015/099947 priority Critical patent/WO2017113218A1/en
Publication of WO2017113218A1 publication Critical patent/WO2017113218A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
    • B28B3/20—Producing shaped articles from the material by using presses; Presses specially adapted therefor wherein the material is extruded
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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

Definitions

  • the invention relates to the technical field of dielectric resonators, in particular to a microwave dielectric ceramic material and a preparation method thereof, a resonator, a cavity filter and a radio frequency remote device.
  • the dielectric resonator is a basic microwave component.
  • the dielectric resonator can be used to form microwave circuits such as filters, oscillators and antennas. It is widely used in mobile communication, satellite communication, military radar, global positioning system, Bluetooth technology, wireless LAN, etc. In modern communication, it is the key infrastructure of modern communication technology.
  • dielectric resonators used in microwave circuits must meet the following dielectric performance requirements: (1) have a relatively high dielectric constant ⁇ r at microwave frequencies, and generally require ⁇ r >20 In order to miniaturize and integrate the microwave device; (2) have a very low dielectric loss at the microwave resonant frequency, that is, a high quality factor (Q ⁇ f), to ensure excellent frequency selection characteristics and reduce device Insertion loss at high frequencies; (3) Temperature coefficient of resonance frequency ( ⁇ f ) close to zero to ensure high stability of the resonant frequency of the device in a temperature changing environment.
  • dopants such as Mn, Sn, Zr, Ca, Sr, and Pb on the dielectric properties of Ba 2 Ti 9 O 20 have also been studied. The results show that doping Mn, Sn, Pb will seriously reduce the Q ⁇ f value, while doping Zr, Ca, Sr can increase the Q ⁇ f value.
  • the Ba 2 Ti 9 O 20 based dielectric ceramic material resonator is mainly a dry press molding method.
  • the cited documents are as follows:
  • the dielectric constant ⁇ r of the Ba 2 Ti 9 O 20 based dielectric ceramic material prepared by the dry pressing method is low, which is not conducive to miniaturization and integration of the microwave device; the quality factor is low, and the dielectric loss is high, and the resonance
  • the frequency temperature coefficient ( ⁇ f ) is high and there is no guarantee that the resonant frequency of the device will be highly stable in temperature-varying environments. Therefore, the Ba 2 Ti 9 O 20 based dielectric ceramic material resonator prepared by the dry pressing method has poor dielectric properties.
  • the molding process in the prior art is mainly dry press molding.
  • the principle of dry pressing is as follows: the dielectric ceramic powder is granulated by a binder, pressed and formed by a die, and then sintered.
  • the preparation of the dielectric resonator by this process has the following disadvantages: (1) During the press forming process, internal and external friction between the particles and between the particles and the mold wall causes pressure loss to cause uneven force in various portions of the green compact, so green body and sintering The sample density distribution is not uniform.
  • the degree of unevenness is related to the selected pressing method.
  • the common pressing methods are unidirectional pressing and bidirectional pressing.
  • the density distribution is shown in Figures 1a and 1b.
  • the uniformity of density affects the dielectric properties of the dielectric resonator. It also affects the performance of the filter; (2) limited by the pressing method, the dielectric resonator is mostly columnar (or similar), not all shape sizes can be prepared by dry pressing, such as complex shaped resonators. Demolding is difficult to achieve, and resonators with large aspect ratios cannot be produced by pressing, because low density regions are likely to occur due to uneven density, which causes distortion of the resonator during sintering, resulting in poor precision in order to obtain a desired shape. Or the size also needs to be machined.
  • the density of the resonators of the prepared microwave dielectric ceramic material is not uniform, resulting in poor dielectric properties of the microwave dielectric ceramic resonator;
  • the dry pressing method cannot prepare a resonator with a complicated shape.
  • the embodiment of the invention provides a Ba 2 Ti 9 O 20 based microwave dielectric ceramic material resonator and a preparation method thereof, so as to solve the density unevenness of the microwave dielectric ceramic prepared by the dry pressing method in the prior art, resulting in the use of the microwave
  • the dielectric ceramic is made into a technical problem that the dielectric properties of the resonator are poor.
  • an aspect of the present invention provides a method for preparing a Ba 2 Ti 9 O 20 based microwave dielectric ceramic material resonator.
  • the preparation method includes:
  • the embryo body is subjected to non-polar solvent extraction degreasing and thermal degreasing;
  • the thermally degreased green body is sintered to obtain the Ba 2 Ti 9 O 20 based microwave dielectric ceramic.
  • the Ba 2 Ti 9 O 20 -based ceramic powder in the mixture has a weight percentage of 76 to 85%, and the organic binder has a weight percentage of 15 to 24 %.
  • the Ba 2 Ti 9 O 20 -based ceramic powder has a formula of Ba 2 Ti 9 O 20 +ax+by, wherein x and y include at least MoO 3 , MnO 2 , WO 3 , One or more of SnO 2 , B 2 O 3 , ZnO, Nb 2 O 5 , ZrO 2 , CaCO 3 , SrCO 3 , and PbCO 3 , 0 mol ⁇ a, b ⁇ 0.20 mol.
  • the organic binder comprises a binder, a surfactant, a low melting organic compound, and a plasticizer.
  • the step of injection molding the mixture comprises:
  • the viscous melt is injected into the mold, and after being cooled in the mold, the mold is released to obtain a green body;
  • the injection temperature is 170 ° C ⁇ 200 ° C.
  • the non-polar solvent extraction degreasing process of the embryo body specifically comprises:
  • the injection-molded body is placed in a non-polar solvent to dissolve and remove part of the organic binder;
  • the non-polar solvent is extracted and the degreased body is dried.
  • the degreased and dried embryo body is subjected to thermal degreasing by extracting the non-polar solvent to remove the remaining organic binder in the embryo body.
  • the thermal degreasing process is: the embryo body The temperature was raised to 550 ° C at a heating rate of 0.5 to 5 ° C / min, and then kept for 2 to 3 hours.
  • the sintering temperature is 1200 to 1400 ° C, and the temperature is maintained for 2 to 6 hours after heating.
  • the temperature of the non-polar solvent in the non-polar solvent extraction degreasing process is 30-50 ° C
  • the degreasing time is 12-36 hours
  • the drying temperature after degreasing is 50- 70 ° C
  • drying time is 4 ⁇ 12h.
  • the weight percentage of each component in the organic binder is: 50 to 90% of the binder; 1 to 5% of the surfactant; 2 to 11% of the low melting point organic substance Plasticizer 1 ⁇ 11%.
  • the binder comprises at least paraffin, ethylene-vinyl acetate copolymer, polypropylene, random polypropylene, polystyrene, polymethacrylate, ethylene ethyl acrylate copolymer.
  • the surfactant at least one or more of stearic acid, octanoic acid, and microcrystalline paraffin;
  • the plasticizer comprising at least dibutyl phthalate, phthalic acid One or more of diethyl ester and dioctyl phthalate.
  • the second aspect of the present invention provides a Ba 2 Ti 9 O 20 based microwave dielectric ceramic material, wherein the microwave dielectric ceramic material comprises Ba 2 Ti 9 O 20 in a weight percentage of 76-85%.
  • the base ceramic powder and the organic binder having a weight percentage of 15 to 24%.
  • the Ba 2 Ti 9 O 20 -based ceramic powder has a formula of Ba 2 Ti 9 O 20 +ax+by, wherein x and y include at least MoO 3 , MnO 2 , WO 3 , One or more of SnO 2 , B 2 O 3 , ZnO, Nb 2 O 5 , ZrO 2 , CaCO 3 , SrCO 3 , and PbCO 3 , 0 mol ⁇ a, b ⁇ 0.20 mol.
  • the organic binder comprises a binder, a surfactant, a low melting organic compound, and a plasticizer.
  • the weight percentage of each component in the organic binder is: 50 to 90% of the binder; 1 to 5% of the surfactant; 2 to 11% of the low melting point organic substance Plasticizer 1 ⁇ 11%.
  • the binder comprises at least paraffin, ethylene-vinyl acetate copolymer, polypropylene, random polypropylene, polystyrene, polymethacrylate, ethylene ethyl acrylate copolymer.
  • the surfactant at least one or more of stearic acid, octanoic acid, and microcrystalline paraffin;
  • the plasticizer comprising at least dibutyl phthalate, phthalic acid One or more of diethyl ester and dioctyl phthalate.
  • a third aspect of the invention provides a resonator which is produced by the production method according to any of the above embodiments.
  • a fourth aspect of the present invention provides a cavity filter including a cavity, a cover plate, and a resonator in the third aspect, the cover plate covering the cavity to form a resonant cavity, The resonator is mounted within the cavity.
  • a fifth aspect of the present invention provides a radio remote device, comprising: a radio frequency transceiver module, a power amplifier module, and a cavity filter according to the fourth aspect, the radio frequency transceiver module and the The power amplifier module is connected, and the power amplifier module is connected to the cavity filter.
  • a sixth aspect of the present invention provides a formulation of a Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material, the formulation comprising the following components by weight: Ba 2 Ti 9 O 20 based ceramic powder 76-85%; organic The binder is 15 to 24%.
  • the Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material provided by the invention and the preparation method of the resonator thereof can obtain uniform density and size distribution by injection molding Ba 2 Ti 9 O 20 based dielectric ceramics.
  • the microwave dielectric ceramic material, the resonator made of the microwave dielectric ceramic material not only has high dimensional accuracy, but also has a high dielectric constant ⁇ r, a high quality factor Q ⁇ f value and a low temperature coefficient of resonance frequency ( ⁇ f) and the like, thereby making the prepared cavity filter have better dielectric properties and stability.
  • Figure 1a is a density distribution diagram of a unidirectionally pressed sample prepared by dry pressing
  • Figure 1b is a density distribution diagram of a biaxially compressed sample prepared by dry pressing
  • FIG. 2 is a schematic flow chart of a preferred embodiment of a method for preparing a Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material resonator according to the present invention
  • Figure 3a is an electron microscope scan of the Ba 2 Ti 9 O 20 based dielectric resonator port after dry pressing
  • Figure 3b is an electron microscope scan of the mouthpiece of the Ba 2 Ti 9 O 20 based dielectric resonator prepared by injection molding;
  • FIG. 4 is a block diagram showing the structural composition of a preferred embodiment of the radio remote device of the present invention.
  • FIG. 2 is a schematic flow chart of a preferred embodiment of a method for preparing a Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material according to the present invention; the preparation method includes but is not limited to the following steps:
  • step S100 a mixture is prepared.
  • the mixture includes at least Ba 2 Ti 9 O 20 based ceramic powder and an organic binder.
  • the Ba 2 Ti 9 O 20 -based ceramic powder and the organic binder are mixed on a kneader until the mixing is uniform, and the mixing time is preferably 4 to 8 hours to obtain an injection molding mixture, which is mixed.
  • the content of different components is related to the particle size, morphology and density of the powder, so different powders have different mixture formulations; for the Ba 2 Ti 9 O 20 based dielectric ceramics in the present invention, in the injection molding mixture, Ba 2 Ti
  • the weight percentage of the 9 O 20 -based ceramic powder is preferably 76 to 85%, and the weight percentage of the organic binder is preferably 15 to 24%.
  • the Ba 2 Ti 9 O 20 -based microwave dielectric ceramic prepared by using the Ba 2 Ti 9 O 20 -based ceramic powder in a weight percentage content has excellent dielectric properties and quality stability.
  • the formula of Ba 2 Ti 9 O 20 -based ceramic powder is Ba 2 Ti 9 O 20 +ax+by, and x and y include at least MoO 3 , MnO 2 , WO 3 , SnO 2 , B 2 O 3 , ZnO One or more of Nb 2 O 5 , ZrO 2 , CaCO 3 , SrCO 3 , and PbCO 3 , and a and b in the chemical formula preferably have a value range of 0 mol ⁇ a, b ⁇ 0.20 mol.
  • the microwave dielectric ceramic material obtained by injection molding can have a high dielectric constant ⁇ r, a high quality factor Q ⁇ f value, and Lower resonant frequency temperature coefficient ( ⁇ f).
  • the formulation of the Ba 2 Ti 9 O 20 group is determined mainly by the solid phase method, and is proportioned, generally BaCO 3 and TiO 2 are obtained in a ratio of 1:4, and then ball milled and calcined. (calcination temperature is 1000 ° C ⁇ 1200 ° C) and milling; wherein, the ball-milling medium when the calcined (ie, after the reaction) powder is placed in a ball mill for ball milling is a zirconia ball, the ball milling time is 4 to 12 h, during the ball milling process Add 2% to 5% of PVA (polyvinyl alcohol) binder, granulate on a spray tower, and then put the granulated powder into a mold for press molding (pressure is 100 MPa to 200 MPa) to calcine the test material itself. The properties are finally ground and pulverized by a grinder to obtain the desired Ba 2 Ti 9 O 20 -based microwave dielectric material.
  • PVA polyvinyl alcohol
  • the organic binder may include a binder, a surfactant, a low melting point organic substance, a plasticizer, and the like.
  • the weight percentage of each component in the organic binder is preferably: 50 to 90% of the binder; 1 to 5% of the surfactant; 2 to 11% of the low melting organic substance; and 1 to 11% of the plasticizer.
  • the binder comprises at least one or more of paraffin, ethylene-vinyl acetate copolymer, polypropylene, random polypropylene, polystyrene, polymethacrylate, ethylene ethyl acrylate copolymer
  • the surfactant includes at least one or more of stearic acid, octanoic acid, and microcrystalline paraffin;
  • the plasticizer includes at least dibutyl phthalate, diethyl phthalate, dioctyl phthalate One or more of the fats.
  • step S200 the mixture is injection molded to obtain a green body.
  • the step S200 further comprises: heating the mixture into a viscous melt in an injection molding machine; then injecting the viscous melt into the mold, cooling in the mold, and demolding to obtain a green body.
  • the injection temperature is preferably from 170 ° C to 200 ° C, and the viscous melt is injected into the mold and released from the mold in 2 to 4 minutes to obtain a green body.
  • the injection temperature and the cooling time in this step can make the density and size distribution of the obtained microwave dielectric ceramic material more uniform, and the performance is more stable.
  • step S300 the embryo body is subjected to non-polar solvent extraction degreasing and thermal degreasing.
  • the non-polar solvent extraction degreasing process is as follows: the injection-molded body is placed in a non-polar solvent such as gasoline, carbon disulfide, xylene, diethyl ether, really, chloroform, carbon tetrachloride or naphtha to dissolve and remove
  • a non-polar solvent such as gasoline, carbon disulfide, xylene, diethyl ether, really, chloroform, carbon tetrachloride or naphtha to dissolve and remove
  • the temperature of the partially organic binder, the non-polar solvent is preferably controlled between 30 and 50 ° C, and the degreasing time is between 12 and 36 hours.
  • the non-polar solvent extract degreased body is sufficiently dried in an oven, and the drying temperature is preferably 50 to 70 ° C for 4 to 12 hours.
  • the non-polar solvent extraction degreasing process in this step is very necessary because if the direct thermal desorption occurs, the sample is decomposed during the degreasing process due to the excessively high organic binder component in the embryo body.
  • the thermal degreasing process is as follows: the dried body is placed in an electric heating furnace for thermal degreasing to remove the remaining organic binder.
  • the process is to raise the embryo body to a temperature of 550 ° C at a temperature increase rate of 0.5 to 5 ° C / min, followed by incubation for 2 to 3 hours.
  • the heating rate and holding time parameters in this step can ensure that the obtained microwave dielectric ceramic material has a dense structure without cracks and further improves the stability of performance under the premise of satisfying the production efficiency.
  • step S400 the thermally degreased green body is sintered to obtain a Ba 2 Ti 9 O 20 based microwave dielectric ceramic.
  • the sintering temperature is preferably between 1200 and 1400 ° C and the temperature is maintained for 2 to 6 hours.
  • the invention provides a Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material by injection molding, and a microwave dielectric ceramic material having uniform density and size distribution can be obtained by injection molding a Ba 2 Ti 9 O 20 based dielectric ceramic, and the microwave medium is used.
  • the resonator made of ceramic material not only has high dimensional accuracy, but also has the advantages of high dielectric constant ⁇ r, high quality factor Q ⁇ f value and low resonance frequency temperature coefficient ( ⁇ f).
  • the main material formulation of this embodiment adopts a chemical formula: Ba 2 Ti 9 O 20 + 0.5 mol% ZrO 2 as a chemical composition, and compares the performance of the dielectric resonator prepared by the dry pressing method and the injection molding method, respectively, and the main material itself of the present embodiment is introduced.
  • the electrical property relative permittivity ⁇ r was 40
  • the quality factor (Q ⁇ f) value was 43500 GHz
  • the resonance frequency temperature coefficient tf was +3 ppm/°C.
  • the Ba2Ti9O20 based dielectric resonator prepared by the injection molding process is realized by the following process steps:
  • (1) Mixed ceramic powder and organic binder Ba 2 Ti 9 O 20 based ceramic powder and organic binder are uniformly mixed to obtain an injection molding mixture, and the content of different components in the mixture is the same as the particle size and shape of the powder. Appearance and density are related, so different powders have different mixture formulations; for Ba 2 Ti 9 O 20 based dielectric ceramics, the Ba 2 Ti 9 O 20 based ceramic powder has a weight percentage of 78 in the injection molding mixture.
  • the organic binder has a weight percentage of 22%; wherein the organic binder is composed of a binder, a surfactant, a low melting point organic substance and a plasticizer, and the weight percentage of each component is: 80% of the binder; surfactant: 5%; low melting point organic: 10%; plasticizer: 5%;
  • injection molding mixture is injection molded on an injection molding machine to obtain a green body, the injection temperature is 180 ° C, and the mold is released after being injected into the mold within 2 minutes;
  • Non-polar solvent extraction degreasing the injection-molded body is placed in a non-polar solvent to dissolve and remove part of the organic binder.
  • the temperature of the non-polar solvent is 30 ° C, and the degreasing time is 24 hours.
  • the non-polar solvent extraction degreased body is sufficiently dried in an oven.
  • the dried body is placed in an electric heating furnace for thermal degreasing to remove the remaining organic binder.
  • the temperature is raised to 550 ° C at a heating rate of 0.5 ° C / min. Keep warm for 2 hours.
  • 60 dielectric resonators were prepared by dry pressing and injection molding respectively.
  • the sample is shown in Fig. 3. It can be seen from Fig. 3 that the injection molding is more uniform in grain size and the particle size is better than that prepared by dry pressing. Small, this is positively correlated with the final performance and stability of the Ba 2 Ti 9 O 20 based dielectric resonator product. At the same time, the performance of the sample was tested. The performance is shown in Table 1:
  • Table 1 Comparison of performance parameters of dielectric resonators prepared by injection molding and dry compression molding
  • the main material formulation of this embodiment adopts a chemical formula: Ba 2 Ti 9 O 20 +1 mol% ZrO 2 as a chemical composition, and compares the performance of the dielectric resonator prepared by the dry pressing method and the injection molding method, respectively, and the dielectric of the main material itself in this embodiment
  • the performance relative permittivity ⁇ r was 39
  • the quality factor (Q ⁇ f) value was 50070 GHz
  • the resonance frequency temperature coefficient ⁇ f was -5 ppm / ° C.
  • the dry pressing method mainly obtains a dielectric resonator by granulation, press molding, and sintering, and the process is simple.
  • the Ba 2 Ti 9 O 20 based dielectric resonator prepared by the injection molding process is realized by the following process steps:
  • the Ba 2 Ti 9 O 20 -based ceramic powder has a weight percentage of 75%, and the weight percentage of the organic binder The content is 25%; the weight percentage of each component in the organic binder is 80% of the binder; 5% of the surfactant; 10% of the low melting organic substance; 5% of the plasticizer.
  • injection molding The injection molding mixture was injection molded on an injection molding machine to obtain a green body, and the injection temperature was 180 ° C. After injection into the mold, the molded body was released in 2 minutes.
  • Non-polar solvent extraction degreasing the injection-molded body is placed in a non-polar solvent to dissolve and remove part of the organic binder.
  • the temperature of the non-polar solvent is 30 ° C, and the degreasing time is 24 hours.
  • the non-polar solvent extraction degreased body is dried in an oven.
  • the dried body is placed in an electric heating furnace for thermal degreasing to remove the remaining organic binder.
  • the temperature is raised to 550 ° C at a heating rate of 0.5 ° C / min. Keep warm for 2 hours.
  • Table 2 Comparison of performance parameters of dielectric resonators prepared by injection molding and dry compression molding
  • the main material formulation of this embodiment adopts a chemical formula: Ba 2 Ti 9 O 20 + 2 mol% ZrO 2 as a chemical composition, and compares the performance of the dielectric resonator prepared by the dry pressing method and the injection molding method, respectively, and the dielectric of the main material itself in this embodiment
  • the performance relative permittivity ⁇ r is 40
  • the quality factor (Q ⁇ f) value is 56000 GHz
  • the resonance frequency temperature coefficient ⁇ f is +2 ppm / ° C.
  • the dry pressing method mainly obtains a dielectric resonator by granulation, press molding, and sintering, and the process is simple.
  • the Ba 2 Ti 9 O 20 based dielectric resonator prepared by the injection molding process is realized by the following process steps:
  • the Ba 2 Ti 9 O 20 -based ceramic powder has a weight percentage of 75%, and the weight percentage of the organic binder The content is 25%; the weight percentage of each component in the organic binder is 80% of the binder; 5% of the surfactant; 10% of the low melting organic substance; 5% of the plasticizer.
  • injection molding The injection molding mixture was injection molded on an injection molding machine to obtain a green body, and the injection temperature was 180 ° C. After injection into the mold, the molded body was released in 2 minutes.
  • Non-polar solvent extraction degreasing the injection-molded body is placed in a non-polar solvent to dissolve and remove part of the organic binder.
  • the temperature of the non-polar solvent is 30 ° C, and the degreasing time is 24 hours.
  • the non-polar solvent extraction degreased body is dried in an oven.
  • the dried body is placed in an electric heating furnace for thermal degreasing to remove the remaining organic binder.
  • the temperature is raised to 550 ° C at a heating rate of 0.5 ° C / min. Keep warm for 2 hours.
  • the preparation method of the Ba 2 Ti 9 O 20 based microwave dielectric ceramic material resonator provided by the invention can obtain the uniformity of density and size distribution and high dimensional accuracy after sintering by injection molding Ba 2 Ti 9 O 20 based dielectric ceramic.
  • the resonator has a low material cost and a simple preparation process. It also has a high quality factor Q x f value and performance stability compared to dry pressed resonators.
  • an embodiment of the present invention further provides a resonator and a cavity filter which are prepared by the preparation method described in the above embodiments.
  • the dielectric resonator of the Ba 2 Ti 9 O 20 -based material is prepared by the dry pressing method and the injection molding method, respectively, and the Q value of the dielectric resonator prepared by the dry pressing method is 3500 to 4200, and the frequency is It is 1.6G, and the dielectric resonator prepared by injection molding has a Q value of 3900 to 4300 and a frequency of 1.6G.
  • the dielectric resonator of the Ba 2 Ti 9 O 20 based material prepared by injection molding in the present invention has a higher Q value and more stable performance.
  • the cavity filter includes the resonator in the above embodiment, and the cavity has a higher quality factor Q ⁇ f value and a lower temperature coefficient of resonance frequency ( ⁇ f), so that the cavity filter prepared by the cavity filter is prepared.
  • the wave device has better dielectric properties and stability. The technical features of the structure and parameters of other parts of the cavity filter are within the understanding of those skilled in the art, and are not described herein again.
  • FIG. 4 is a structural block diagram of a preferred embodiment of the radio remote device of the present invention.
  • the radio remote device includes but is not limited to the following structural units: a radio frequency transceiver module 510, a power amplifier module 520, and a cavity filter. 530.
  • the radio frequency transceiver module 510 is connected to the power amplifier module 520, and the power amplifier module 520 is further connected to the cavity filter 530.
  • the transmit signals from the two channels of the radio transceiver module 510 enter the cavity filter 530 through the power amplifier module 520, and the cavity filter 530 filters the transmit signal, and then the power is synthesized.
  • the RF remote device operates in the uplink time slot, and the signal received from the antenna port is filtered by the cavity filter 530 and then enters the power amplifier module 520, and is amplified by the power amplifier module 520 and output to the RF transceiver.
  • the receiving channel corresponding to module 510.
  • the radio remote device may further include a power module 540, and the power module 540 is configured to supply power to each module of the radio remote device.

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Abstract

Provided in the present invention are a Ba2Ti9O20-based microwave dielectric ceramic material and a preparation method therefor, a resonator, a filter, and a radio frequency remote device, the preparation method for the dielectric ceramic material comprising the steps of: preparing a mixture comprising at least a Ba2Ti9O20-based ceramic powder and an organic binder; injection-molding the mixture to obtain a green body; degreasing and thermally degreasing the green body by using a non-polar solvent extraction method; and sintering the thermally degreased green body to obtain a Ba2Ti9O20-based microwave dielectric ceramic. In the preparation method, Ba2Ti9O20-based dielectric ceramic is injection-molded, resulting in a medium ceramic material with even distribution of density and size as well as a high degree of size precision after sintering. Furthermore, the material cost is low, and the preparation process is simple. Compared with resonator prepared by dry pressing, the ceramic material features a high quality factor (Q×f value) and stable performance.

Description

陶瓷材料及其制备方法、谐振器、滤波器及射频拉远设备Ceramic material and preparation method thereof, resonator, filter and radio remote device 【技术领域】[Technical Field]
本发明涉及介质谐振器的技术领域，具体是涉及一种微波介质陶瓷材料及其制备方法、谐振器、腔体滤波器及射频拉远设备。The invention relates to the technical field of dielectric resonators, in particular to a microwave dielectric ceramic material and a preparation method thereof, a resonator, a cavity filter and a radio frequency remote device.
【背景技术】【Background technique】
介质谐振器是一个最基本的微波元件，利用介质谐振器可以构成滤波器、振荡器和天线等微波电路，广泛应用于移动通讯、卫星通信、军用雷达、全球定位系统、蓝牙技术、无线局域网等现代通信中，是现代通信技术的关键基础器件。应用于微波电路的介质谐振器，除了必备的机械强度外，还需满足如下介电性能要求：(1)在微波频率下具有相对较高的介电常数εr，一般要求εr＞20，以便于微波器件小型化、集成化；(2)在微波谐振频率下具有极低的介电损耗，即很高的品质因数(Q×f)，以保证优良的选频特性和降低器件在高频下的插入损耗；(3)接近零的谐振频率温度系数(τf)，以保证器件在温度变化环境中谐振频率的高度稳定性。The dielectric resonator is a basic microwave component. The dielectric resonator can be used to form microwave circuits such as filters, oscillators and antennas. It is widely used in mobile communication, satellite communication, military radar, global positioning system, Bluetooth technology, wireless LAN, etc. In modern communication, it is the key infrastructure of modern communication technology. In addition to the necessary mechanical strength, dielectric resonators used in microwave circuits must meet the following dielectric performance requirements: (1) have a relatively high dielectric constant ε r at microwave frequencies, and generally require ε r >20 In order to miniaturize and integrate the microwave device; (2) have a very low dielectric loss at the microwave resonant frequency, that is, a high quality factor (Q × f), to ensure excellent frequency selection characteristics and reduce device Insertion loss at high frequencies; (3) Temperature coefficient of resonance frequency (τ f ) close to zero to ensure high stability of the resonant frequency of the device in a temperature changing environment.
Ba2Ti9O20材料的介电性能：εr＝39，Q×f＝32000GHz，τf＝+2ppm/℃。也有人研究了掺杂物如Mn、Sn、Zr、Ca、Sr、Pb对Ba2Ti9O20介电性能的影响。研究结果表明掺杂Mn、Sn、Pb会严重地降低Q×f值，而掺杂Zr、Ca、Sr则能增大Q×f值。Dielectric properties of Ba 2 Ti 9 O 20 material: ε r = 39, Q × f = 32000 GHz, τ f = +2 ppm / °C. The effects of dopants such as Mn, Sn, Zr, Ca, Sr, and Pb on the dielectric properties of Ba 2 Ti 9 O 20 have also been studied. The results show that doping Mn, Sn, Pb will seriously reduce the Q × f value, while doping Zr, Ca, Sr can increase the Q × f value.
根据介质谐振器的性能要求，对Ba2Ti9O20添加不同的化合物。目前制备Ba2Ti9O20基介质陶瓷材料谐振器主要是干压成型法。引用的文献如下：Different compounds are added to Ba 2 Ti 9 O 20 depending on the performance requirements of the dielectric resonator. At present, the Ba 2 Ti 9 O 20 based dielectric ceramic material resonator is mainly a dry press molding method. The cited documents are as follows:
[1]H.M.O’Bryan，J.Thomson Jr，J.K.Plourde，A new BaO-TiO2 compound with temperature-stable high permitivity and lowmicrowave loss，J.Am.Ceram.Soc.，57 450-453(1974).[1] H. M. O'Bryan, J. Thomson Jr, J. K. Plourde, A new BaO-TiO2 compound with temperature-stable high permitivity and low microwave loss, J. Am. Ceram. Soc., 57 450-453 (1974).
[2]J.K.Plourde，D.F.Lim，H.M.O’Bryan，J.Thomson Jr.，Ba2Ti9O20 as a microwave dielectric resonator，J.Amer.Ceram.Soc.，58 418-420(1975).[2] J. K. Plourde, D. F. Lim, H. M. O'Bryan, J. Thomson Jr., Ba 2 Ti 9 O 20 as a microwave dielectric resonator, J. Amer. Ceram. Soc., 58 418-420 (1975).
目前利用干压法制备的Ba2Ti9O20基介质陶瓷材料谐振器介电常数εr较低，不利于微波器件小型化、集成化；品质因数较低，从而介电损耗较高，谐振频率温度系数(τf)较高，无法保证保证器件在温度变化环境中谐振频率的高度稳 定性。因此，利用干压法制备的Ba2Ti9O20基介质陶瓷材料谐振器介电性能较差。At present, the dielectric constant ε r of the Ba 2 Ti 9 O 20 based dielectric ceramic material prepared by the dry pressing method is low, which is not conducive to miniaturization and integration of the microwave device; the quality factor is low, and the dielectric loss is high, and the resonance The frequency temperature coefficient (τ f ) is high and there is no guarantee that the resonant frequency of the device will be highly stable in temperature-varying environments. Therefore, the Ba 2 Ti 9 O 20 based dielectric ceramic material resonator prepared by the dry pressing method has poor dielectric properties.
虽然注射成型的研究和应用在不断的发展，从聚合物到金属再到陶瓷(主要应用于结构陶瓷，氧化铝、氧化锆等)。但对于介质陶瓷谐振器的注射成型研究和生产几乎没有。现有技术中的成型工艺主要是干压成型。干压成型的原理是：对介质陶瓷粉末加粘结剂造粒、通过模具进行压制成型后进行烧结。此工艺制备介质谐振器存在如下缺点：(1)压制成型过程中，颗粒间以及颗粒与模壁间存在的内、外摩擦引起压力损失使压坯各部位受力不均，因此生坯、烧结样品密度分布不均匀。不均匀的程度与选用的压制方式有关，常用的压制方式有单向压制和双向压制，其密度分布情况如图1a和1b所示，密度的均匀性会影响介质谐振器的介电性能，进而也会影响滤波器的工作性能；(2)受限于压制方式，介质谐振器大部分是柱状(或类似形状)，并不是所有形状尺寸能用干压法进行制备，比如形状复杂的谐振器脱模难以实现，长径比大的谐振器也无法通过压制制得，因为容易因密度不均匀而出现低密度区，进而导致烧结过程中谐振器变形，制作精度差，为了得到想要的形状或尺寸还需要进行机加工获得。Although the research and application of injection molding is constantly evolving, from polymers to metals to ceramics (mainly used in structural ceramics, alumina, zirconia, etc.). However, there is almost no research and production of injection molding for dielectric ceramic resonators. The molding process in the prior art is mainly dry press molding. The principle of dry pressing is as follows: the dielectric ceramic powder is granulated by a binder, pressed and formed by a die, and then sintered. The preparation of the dielectric resonator by this process has the following disadvantages: (1) During the press forming process, internal and external friction between the particles and between the particles and the mold wall causes pressure loss to cause uneven force in various portions of the green compact, so green body and sintering The sample density distribution is not uniform. The degree of unevenness is related to the selected pressing method. The common pressing methods are unidirectional pressing and bidirectional pressing. The density distribution is shown in Figures 1a and 1b. The uniformity of density affects the dielectric properties of the dielectric resonator. It also affects the performance of the filter; (2) limited by the pressing method, the dielectric resonator is mostly columnar (or similar), not all shape sizes can be prepared by dry pressing, such as complex shaped resonators. Demolding is difficult to achieve, and resonators with large aspect ratios cannot be produced by pressing, because low density regions are likely to occur due to uneven density, which causes distortion of the resonator during sintering, resulting in poor precision in order to obtain a desired shape. Or the size also needs to be machined.
综上所述，现有技术中通常采用的干压法制备的微波介质陶瓷，存在所制备微波介质陶瓷材料谐振器的密度不均匀，导致微波介质陶瓷材料谐振器介电性能较差；同时，干压法无法制备形状复杂的谐振器。In summary, in the microwave dielectric ceramics prepared by the dry pressing method generally used in the prior art, the density of the resonators of the prepared microwave dielectric ceramic material is not uniform, resulting in poor dielectric properties of the microwave dielectric ceramic resonator; The dry pressing method cannot prepare a resonator with a complicated shape.
【发明内容】[Summary of the Invention]
本发明实施例提供一种Ba2Ti9O20基微波介质陶瓷材料谐振器及其制备方法，以解决现有技术中采用干压成型法制得的微波介质陶瓷的密度不均，导致使用该微波介质陶瓷做成谐振器的介电性能较差的技术问题。The embodiment of the invention provides a Ba 2 Ti 9 O 20 based microwave dielectric ceramic material resonator and a preparation method thereof, so as to solve the density unevenness of the microwave dielectric ceramic prepared by the dry pressing method in the prior art, resulting in the use of the microwave The dielectric ceramic is made into a technical problem that the dielectric properties of the resonator are poor.
为解决上述问题，本发明一方面提供了一种Ba2Ti9O20基微波介质陶瓷材料谐振器的制备方法所述制备方法包括：In order to solve the above problems, an aspect of the present invention provides a method for preparing a Ba 2 Ti 9 O 20 based microwave dielectric ceramic material resonator. The preparation method includes:
制备混合料，所述混合料中至少包括Ba2Ti9O20基陶瓷粉体和有机粘结剂；Preparing a mixture comprising at least Ba 2 Ti 9 O 20 based ceramic powder and an organic binder;
将所述混合料注射成型，得到坯体；Injection molding the mixture to obtain a green body;
将所述胚体先后进行非极性溶剂萃取脱脂和热脱脂；The embryo body is subjected to non-polar solvent extraction degreasing and thermal degreasing;
将热脱脂后的坯体进行烧结，以得到所述Ba2Ti9O20基微波介质陶瓷。The thermally degreased green body is sintered to obtain the Ba 2 Ti 9 O 20 based microwave dielectric ceramic.
根据本发明一优选实施例，所述混合料中的Ba2Ti9O20基陶瓷粉体的重量百分含量为76～85％，所述有机粘结剂的重量百分含量为15～24％。 According to a preferred embodiment of the present invention, the Ba 2 Ti 9 O 20 -based ceramic powder in the mixture has a weight percentage of 76 to 85%, and the organic binder has a weight percentage of 15 to 24 %.
根据本发明一优选实施例，所述Ba2Ti9O20基陶瓷粉体的配方化学式为Ba2Ti9O20+ax+by，其中x、y至少包括MoO3、MnO2、WO3、SnO2、B2O3、ZnO、Nb2O5、ZrO2、CaCO3、SrCO3、PbCO3中的一种或多种，0mol≤a，b≤0.20mol。According to a preferred embodiment of the present invention, the Ba 2 Ti 9 O 20 -based ceramic powder has a formula of Ba 2 Ti 9 O 20 +ax+by, wherein x and y include at least MoO 3 , MnO 2 , WO 3 , One or more of SnO 2 , B 2 O 3 , ZnO, Nb 2 O 5 , ZrO 2 , CaCO 3 , SrCO 3 , and PbCO 3 , 0 mol ≤ a, b ≤ 0.20 mol.
根据本发明一优选实施例，所述有机粘结剂包括粘结剂、表面活性剂、低熔点有机物以及增塑剂。According to a preferred embodiment of the invention, the organic binder comprises a binder, a surfactant, a low melting organic compound, and a plasticizer.
根据本发明一优选实施例，所述将混合料注射成型的步骤包括：According to a preferred embodiment of the invention, the step of injection molding the mixture comprises:
将所述混合料在注射成型机中加热成粘稠性熔体；Heating the mixture into a viscous melt in an injection molding machine;
将所述粘稠性熔体注入模具内，在模具内冷却后脱模得到坯体；The viscous melt is injected into the mold, and after being cooled in the mold, the mold is released to obtain a green body;
其中，注射温度为170℃～200℃。Among them, the injection temperature is 170 ° C ~ 200 ° C.
根据本发明一优选实施例，所述胚体的非极性溶剂萃取脱脂过程具体包括：According to a preferred embodiment of the present invention, the non-polar solvent extraction degreasing process of the embryo body specifically comprises:
将注射成型得到的坯体放入非极性溶剂中，以溶解脱除部分有机粘结剂；The injection-molded body is placed in a non-polar solvent to dissolve and remove part of the organic binder;
将非极性溶剂萃取脱脂后的坯体进行干燥。The non-polar solvent is extracted and the degreased body is dried.
根据本发明一优选实施例，将经由非极性溶剂萃取脱脂并干燥的胚体继续进行热脱脂，以脱除胚体中剩余的有机粘结剂，所述热脱脂的过程为：将胚体以0.5～5℃/min的升温速率升温至550℃，然后保温2～3小时。According to a preferred embodiment of the present invention, the degreased and dried embryo body is subjected to thermal degreasing by extracting the non-polar solvent to remove the remaining organic binder in the embryo body. The thermal degreasing process is: the embryo body The temperature was raised to 550 ° C at a heating rate of 0.5 to 5 ° C / min, and then kept for 2 to 3 hours.
根据本发明一优选实施例，所述烧结的温度为1200～1400℃，加热后保温2～6小时。According to a preferred embodiment of the present invention, the sintering temperature is 1200 to 1400 ° C, and the temperature is maintained for 2 to 6 hours after heating.
根据本发明一优选实施例，所述胚体非极性溶剂萃取脱脂过程中的非极性溶剂的温度为30～50℃，脱脂时间为12～36小时；脱脂后进行干燥的温度为50～70℃，干燥时间为4～12h。According to a preferred embodiment of the present invention, the temperature of the non-polar solvent in the non-polar solvent extraction degreasing process is 30-50 ° C, the degreasing time is 12-36 hours, and the drying temperature after degreasing is 50- 70 ° C, drying time is 4 ~ 12h.
根据本发明一优选实施例，所述有机粘结剂中各组分的重量百分含量为：粘结剂50～90％；表面活性剂1～5％；低熔点有机物2～11％以及增塑剂1～11％。According to a preferred embodiment of the present invention, the weight percentage of each component in the organic binder is: 50 to 90% of the binder; 1 to 5% of the surfactant; 2 to 11% of the low melting point organic substance Plasticizer 1 ~ 11%.
根据本发明一优选实施例，所述粘结剂至少包括石蜡、乙烯-乙酸乙烯脂共聚物、聚丙烯、无规聚丙烯、聚苯乙烯、聚甲基丙烯酸酯、乙烯丙烯酸乙酯共聚物中的一种或多种；所述表面活性剂至少包括硬脂酸、辛酸、微晶石蜡中的一种或多种；所述增塑剂至少包括邻苯二甲酸二丁酯、邻苯二甲酸二乙酯、邻苯二甲酸二辛脂中的一种或多种。According to a preferred embodiment of the present invention, the binder comprises at least paraffin, ethylene-vinyl acetate copolymer, polypropylene, random polypropylene, polystyrene, polymethacrylate, ethylene ethyl acrylate copolymer. One or more; the surfactant at least one or more of stearic acid, octanoic acid, and microcrystalline paraffin; the plasticizer comprising at least dibutyl phthalate, phthalic acid One or more of diethyl ester and dioctyl phthalate.
为解决上述技术问题，本发明第二方面提供一种Ba2Ti9O20基微波介质陶瓷材料，所述微波介质陶瓷材料中包括重量百分含量为76～85％的Ba2Ti9O20基陶瓷粉体以及重量百分含量为15～24％的有机粘结剂。In order to solve the above technical problem, the second aspect of the present invention provides a Ba 2 Ti 9 O 20 based microwave dielectric ceramic material, wherein the microwave dielectric ceramic material comprises Ba 2 Ti 9 O 20 in a weight percentage of 76-85%. The base ceramic powder and the organic binder having a weight percentage of 15 to 24%.
根据本发明一优选实施例，所述Ba2Ti9O20基陶瓷粉体的配方化学式为 Ba2Ti9O20+ax+by，其中x、y至少包括MoO3、MnO2、WO3、SnO2、B2O3、ZnO、Nb2O5、ZrO2、CaCO3、SrCO3、PbCO3中的一种或多种，0mol≤a，b≤0.20mol。According to a preferred embodiment of the present invention, the Ba 2 Ti 9 O 20 -based ceramic powder has a formula of Ba 2 Ti 9 O 20 +ax+by, wherein x and y include at least MoO 3 , MnO 2 , WO 3 , One or more of SnO 2 , B 2 O 3 , ZnO, Nb 2 O 5 , ZrO 2 , CaCO 3 , SrCO 3 , and PbCO 3 , 0 mol ≤ a, b ≤ 0.20 mol.
根据本发明一优选实施例，所述有机粘结剂包括粘结剂、表面活性剂、低熔点有机物以及增塑剂。According to a preferred embodiment of the invention, the organic binder comprises a binder, a surfactant, a low melting organic compound, and a plasticizer.
根据本发明一优选实施例，所述有机粘结剂中各组分的重量百分含量为：粘结剂50～90％；表面活性剂1～5％；低熔点有机物2～11％以及增塑剂1～11％。According to a preferred embodiment of the present invention, the weight percentage of each component in the organic binder is: 50 to 90% of the binder; 1 to 5% of the surfactant; 2 to 11% of the low melting point organic substance Plasticizer 1 ~ 11%.
根据本发明一优选实施例，所述粘结剂至少包括石蜡、乙烯-乙酸乙烯脂共聚物、聚丙烯、无规聚丙烯、聚苯乙烯、聚甲基丙烯酸酯、乙烯丙烯酸乙酯共聚物中的一种或多种；所述表面活性剂至少包括硬脂酸、辛酸、微晶石蜡中的一种或多种；所述增塑剂至少包括邻苯二甲酸二丁酯、邻苯二甲酸二乙酯、邻苯二甲酸二辛脂中的一种或多种。According to a preferred embodiment of the present invention, the binder comprises at least paraffin, ethylene-vinyl acetate copolymer, polypropylene, random polypropylene, polystyrene, polymethacrylate, ethylene ethyl acrylate copolymer. One or more; the surfactant at least one or more of stearic acid, octanoic acid, and microcrystalline paraffin; the plasticizer comprising at least dibutyl phthalate, phthalic acid One or more of diethyl ester and dioctyl phthalate.
本发明第三方面提供一种谐振器，所述谐振器由上述实施例中的任一项所述的制备方法制得。A third aspect of the invention provides a resonator which is produced by the production method according to any of the above embodiments.
本发明第四方面提供一种腔体滤波器，所述腔体滤波器包括腔体、盖板以及第三方面中的谐振器，所述盖板封盖所述腔体以形成谐振腔，所述谐振器安装在所述腔体内。A fourth aspect of the present invention provides a cavity filter including a cavity, a cover plate, and a resonator in the third aspect, the cover plate covering the cavity to form a resonant cavity, The resonator is mounted within the cavity.
本发明第五方面提供一种射频拉远设备，所述射频拉远设备包括：射频收发信机模块、功放模块以及第四方面所述的腔体滤波器，所述射频收发信机模块与所述功放模块连接，所述功放模块与所述腔体滤波器连接。A fifth aspect of the present invention provides a radio remote device, comprising: a radio frequency transceiver module, a power amplifier module, and a cavity filter according to the fourth aspect, the radio frequency transceiver module and the The power amplifier module is connected, and the power amplifier module is connected to the cavity filter.
本发明第六方面提供一种Ba2Ti9O20基微波介质陶瓷材料的配方，该配方包括以下重量百分含量的组分：Ba2Ti9O20基陶瓷粉体76～85％；有机粘结剂15～24％。A sixth aspect of the present invention provides a formulation of a Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material, the formulation comprising the following components by weight: Ba 2 Ti 9 O 20 based ceramic powder 76-85%; organic The binder is 15 to 24%.
相对于现有技术，本发明提供的Ba2Ti9O20基微波介质陶瓷材料及其谐振器的制备方法，通过将Ba2Ti9O20基介质陶瓷注射成型，可以得到密度和尺寸分布均匀的微波介质陶瓷材料，使用该微波介质陶瓷材料制成的谐振器不但尺寸精度高，还具有较高的介电常数εr、较高的品质因数Q×f值和较低的谐振频率温度系数(τf)等优点，进而使制备得到的腔体滤波器具有较佳的介电性能和稳定性。 Compared with the prior art, the Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material provided by the invention and the preparation method of the resonator thereof can obtain uniform density and size distribution by injection molding Ba 2 Ti 9 O 20 based dielectric ceramics. The microwave dielectric ceramic material, the resonator made of the microwave dielectric ceramic material not only has high dimensional accuracy, but also has a high dielectric constant εr, a high quality factor Q×f value and a low temperature coefficient of resonance frequency ( Τf) and the like, thereby making the prepared cavity filter have better dielectric properties and stability.
【附图说明】[Description of the Drawings]
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅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。In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the present invention. Other drawings may also be obtained from those of ordinary skill in the art in light of the inventive work.
图1a是干压法中的单向压制制备样品的密度分布图；Figure 1a is a density distribution diagram of a unidirectionally pressed sample prepared by dry pressing;
图1b是干压法中的双向压制制备样品的密度分布图；Figure 1b is a density distribution diagram of a biaxially compressed sample prepared by dry pressing;
图2是本发明Ba2Ti9O20基微波介质陶瓷材料谐振器的制备方法一优选实施例的流程示意图；2 is a schematic flow chart of a preferred embodiment of a method for preparing a Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material resonator according to the present invention;
图3a是干压成型制备的Ba2Ti9O20基介质谐振器端口腐蚀后的电子显微镜扫描图；Figure 3a is an electron microscope scan of the Ba 2 Ti 9 O 20 based dielectric resonator port after dry pressing;
图3b是注射成型制备的Ba2Ti9O20基介质谐振器端件口腐蚀后的电子显微镜扫描图；以及Figure 3b is an electron microscope scan of the mouthpiece of the Ba 2 Ti 9 O 20 based dielectric resonator prepared by injection molding;
图4是本发明射频拉远设备一优选实施例的结构组成框图。4 is a block diagram showing the structural composition of a preferred embodiment of the radio remote device of the present invention.
【具体实施方式】【detailed description】
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，所描述的实施例仅是本发明的一部分实施例，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做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention are clearly and completely described in the following with reference to the accompanying drawings in the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
请参阅图2，图2是本发明Ba2Ti9O20基微波介质陶瓷材料的制备方法一优选实施例的流程示意图；该制备方法包括但不限于以下步骤：Please refer to FIG. 2. FIG. 2 is a schematic flow chart of a preferred embodiment of a method for preparing a Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material according to the present invention; the preparation method includes but is not limited to the following steps:
步骤S100，制备混合料。混合料中至少包括Ba2Ti9O20基陶瓷粉体和有机粘结剂。In step S100, a mixture is prepared. The mixture includes at least Ba 2 Ti 9 O 20 based ceramic powder and an organic binder.
在本实施例中，将Ba2Ti9O20基陶瓷粉体和有机粘结剂在混炼机上进行混合，直至混合均匀，优选混合时间为4～8h，得到注射成型混合料，混料中不同成分的含量跟粉末的粒度、形貌、密度有关，所以不同的粉末其混合物配方不同；针对于本发明中的Ba2Ti9O20基介质陶瓷，在注射成型混合料中，Ba2Ti9O20基陶瓷粉体的重量百分含量优选为76～85％，有机粘结剂的重量百分含量优选为 15～24％。采用该重量百分含量Ba2Ti9O20基陶瓷粉体的配置方式制备的Ba2Ti9O20基微波介质陶瓷，具有优良的介电性能和品质稳定性。In the present embodiment, the Ba 2 Ti 9 O 20 -based ceramic powder and the organic binder are mixed on a kneader until the mixing is uniform, and the mixing time is preferably 4 to 8 hours to obtain an injection molding mixture, which is mixed. The content of different components is related to the particle size, morphology and density of the powder, so different powders have different mixture formulations; for the Ba 2 Ti 9 O 20 based dielectric ceramics in the present invention, in the injection molding mixture, Ba 2 Ti The weight percentage of the 9 O 20 -based ceramic powder is preferably 76 to 85%, and the weight percentage of the organic binder is preferably 15 to 24%. The Ba 2 Ti 9 O 20 -based microwave dielectric ceramic prepared by using the Ba 2 Ti 9 O 20 -based ceramic powder in a weight percentage content has excellent dielectric properties and quality stability.
其中，Ba2Ti9O20基陶瓷粉体的配方化学式为Ba2Ti9O20+ax+by，x、y至少包括MoO3、MnO2、WO3、SnO2、B2O3、ZnO、Nb2O5、ZrO2、CaCO3、SrCO3、PbCO3中的一种或多种，而化学式中的a、b的取值范围优选为：0mol≤a，b≤0.20mol。利用本发明中化学式的配比系数的Ba2Ti9O20基陶瓷粉体，可以使注射成型得到的微波介质陶瓷材料具有较高的介电常数εr、较高的品质因数Q×f值以及较低的谐振频率温度系数(τf)。Wherein, the formula of Ba 2 Ti 9 O 20 -based ceramic powder is Ba 2 Ti 9 O 20 +ax+by, and x and y include at least MoO 3 , MnO 2 , WO 3 , SnO 2 , B 2 O 3 , ZnO One or more of Nb 2 O 5 , ZrO 2 , CaCO 3 , SrCO 3 , and PbCO 3 , and a and b in the chemical formula preferably have a value range of 0 mol ≤ a, b ≤ 0.20 mol. By using the Ba 2 Ti 9 O 20 -based ceramic powder of the formula of the chemical formula of the present invention, the microwave dielectric ceramic material obtained by injection molding can have a high dielectric constant εr, a high quality factor Q×f value, and Lower resonant frequency temperature coefficient (τf).
这其中，Ba2Ti9O20基的配方确定主要通过固相法制备获得，按比例配料，一般为BaCO3和TiO2按照1∶4的比例进行配比反应得到，之后再经球磨、煅烧(煅烧温度为1000℃～1200℃)以及碾磨；其中，对煅烧好的(即反应后)粉末放入球磨机进行球磨时的球磨介质为氧化锆球，球磨时间为4～12h，球磨过程中加入2％～5％的PVA(聚乙烯醇)粘结剂，经在喷雾塔上进行造粒，然后将造粒粉末放入模具进行压制成型后(压力为100MPa～200MPa)进行煅烧测试材料本身性能，最终经过研磨机研磨粉碎后得到所需要的Ba2Ti9O20基微波介质材料。Among them, the formulation of the Ba 2 Ti 9 O 20 group is determined mainly by the solid phase method, and is proportioned, generally BaCO 3 and TiO 2 are obtained in a ratio of 1:4, and then ball milled and calcined. (calcination temperature is 1000 ° C ~ 1200 ° C) and milling; wherein, the ball-milling medium when the calcined (ie, after the reaction) powder is placed in a ball mill for ball milling is a zirconia ball, the ball milling time is 4 to 12 h, during the ball milling process Add 2% to 5% of PVA (polyvinyl alcohol) binder, granulate on a spray tower, and then put the granulated powder into a mold for press molding (pressure is 100 MPa to 200 MPa) to calcine the test material itself. The properties are finally ground and pulverized by a grinder to obtain the desired Ba 2 Ti 9 O 20 -based microwave dielectric material.
该有机粘结剂可以包括粘结剂、表面活性剂、低熔点有机物以及增塑剂等。其中，有机粘结剂中各组分的重量百分含量优选为：粘结剂50～90％；表面活性剂1～5％；低熔点有机物2～11％以及增塑剂1～11％。The organic binder may include a binder, a surfactant, a low melting point organic substance, a plasticizer, and the like. Wherein, the weight percentage of each component in the organic binder is preferably: 50 to 90% of the binder; 1 to 5% of the surfactant; 2 to 11% of the low melting organic substance; and 1 to 11% of the plasticizer.
进一步优选地，粘结剂至少包括石蜡、乙烯-乙酸乙烯脂共聚物、聚丙烯、无规聚丙烯、聚苯乙烯、聚甲基丙烯酸酯、乙烯丙烯酸乙酯共聚物中的一种或多种；表面活性剂至少包括硬脂酸、辛酸、微晶石蜡中的一种或多种；增塑剂至少包括邻苯二甲酸二丁酯、邻苯二甲酸二乙酯、邻苯二甲酸二辛脂中的一种或多种。从以上提供的多种粘结剂的种类进行合理选取，在满足材料功能的同时，还可以节省一定成本。Further preferably, the binder comprises at least one or more of paraffin, ethylene-vinyl acetate copolymer, polypropylene, random polypropylene, polystyrene, polymethacrylate, ethylene ethyl acrylate copolymer The surfactant includes at least one or more of stearic acid, octanoic acid, and microcrystalline paraffin; the plasticizer includes at least dibutyl phthalate, diethyl phthalate, dioctyl phthalate One or more of the fats. Reasonable selection of the types of binders provided above can save a certain cost while satisfying the function of the material.
步骤S200，将混合料注射成型，得到坯体。In step S200, the mixture is injection molded to obtain a green body.
步骤S200中进一步包括：将混合料在注射成型机中加热成粘稠性熔体；然后将该粘稠性熔体注入模具内，在模具内冷却后脱模得到坯体。其中，注射温度优选为170℃～200℃，粘稠性熔体注入模具后在2～4分钟内脱模得到成型坯体。该步骤中的注射温度以及冷却时间，可以使得到的微波介质陶瓷材料的密度和尺寸分布更加均匀，进而性能更稳定。The step S200 further comprises: heating the mixture into a viscous melt in an injection molding machine; then injecting the viscous melt into the mold, cooling in the mold, and demolding to obtain a green body. The injection temperature is preferably from 170 ° C to 200 ° C, and the viscous melt is injected into the mold and released from the mold in 2 to 4 minutes to obtain a green body. The injection temperature and the cooling time in this step can make the density and size distribution of the obtained microwave dielectric ceramic material more uniform, and the performance is more stable.
步骤S300，将胚体先后进行非极性溶剂萃取脱脂和热脱脂。 In step S300, the embryo body is subjected to non-polar solvent extraction degreasing and thermal degreasing.
非极性溶剂萃取脱脂过程如下：将注射成型得到的坯体放入汽油、二硫化碳、二甲苯、乙醚、笨、氯仿、四氯化碳、石脑油等非极性溶剂中，以溶解脱除部分有机粘结剂，非极性溶剂的温度优选控制在30～50℃之间，脱脂时间在12～36小时。非极性溶剂萃取脱脂后的坯体在烘箱中充分干燥，干燥温度优选为50～70℃，时间为4～12h。The non-polar solvent extraction degreasing process is as follows: the injection-molded body is placed in a non-polar solvent such as gasoline, carbon disulfide, xylene, diethyl ether, stupid, chloroform, carbon tetrachloride or naphtha to dissolve and remove The temperature of the partially organic binder, the non-polar solvent is preferably controlled between 30 and 50 ° C, and the degreasing time is between 12 and 36 hours. The non-polar solvent extract degreased body is sufficiently dried in an oven, and the drying temperature is preferably 50 to 70 ° C for 4 to 12 hours.
该步骤中的非极性溶剂萃取脱脂过程是非常必要的，因为如果直接进行热脱会由于胚体中有机粘结剂成分过高，而导致样品在脱脂过程中的碎裂。The non-polar solvent extraction degreasing process in this step is very necessary because if the direct thermal desorption occurs, the sample is decomposed during the degreasing process due to the excessively high organic binder component in the embryo body.
热脱脂过程如下：将干燥后的坯体放入电加热炉内进行热脱脂，以脱除剩余的有机粘结剂。该过程优选为将胚体以0.5～5℃/min的升温速率升温至550℃，然后保温2～3小时。该步骤中的升温速率及保温时间参数，在满足生产效率的前提下，可以确保使得到的微波介质陶瓷材料结构致密，不出现裂纹，进一步提升性能的稳定性。The thermal degreasing process is as follows: the dried body is placed in an electric heating furnace for thermal degreasing to remove the remaining organic binder. Preferably, the process is to raise the embryo body to a temperature of 550 ° C at a temperature increase rate of 0.5 to 5 ° C / min, followed by incubation for 2 to 3 hours. The heating rate and holding time parameters in this step can ensure that the obtained microwave dielectric ceramic material has a dense structure without cracks and further improves the stability of performance under the premise of satisfying the production efficiency.
步骤S400，将热脱脂后的坯体进行烧结，以得到Ba2Ti9O20基微波介质陶瓷。In step S400, the thermally degreased green body is sintered to obtain a Ba 2 Ti 9 O 20 based microwave dielectric ceramic.
在该步骤中，烧结温度优选在1200～1400℃之间，保温2～6小时。In this step, the sintering temperature is preferably between 1200 and 1400 ° C and the temperature is maintained for 2 to 6 hours.
本发明用注射成型法制备Ba2Ti9O20基微波介质陶瓷材料，通过将Ba2Ti9O20基介质陶瓷注射成型，可以得到密度和尺寸分布均匀的微波介质陶瓷材料，使用该微波介质陶瓷材料制成的谐振器不但尺寸精度高，还具有较高的介电常数εr、较高的品质因数Q×f值和较低的谐振频率温度系数(τf)等优点。The invention provides a Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material by injection molding, and a microwave dielectric ceramic material having uniform density and size distribution can be obtained by injection molding a Ba 2 Ti 9 O 20 based dielectric ceramic, and the microwave medium is used. The resonator made of ceramic material not only has high dimensional accuracy, but also has the advantages of high dielectric constant εr, high quality factor Q×f value and low resonance frequency temperature coefficient (τf).
下面几个具体实施例来详细说明本发明中Ba2Ti9O20基微波介质陶瓷材料谐振器制作过程和成品谐振器的性能参数。The following specific embodiments will detail the fabrication process of the Ba 2 Ti 9 O 20 based microwave dielectric ceramic material resonator and the performance parameters of the finished resonator in the present invention.
实施例一Embodiment 1
本实施例主材料配方采用化学式：Ba2Ti9O20+0.5mol％ZrO2为化学组成，分别比较干压法和注射成型法制备的介质谐振器的性能，本实施例主材料本身的介电性能相对介电常数εr为40，品质因数(Q×f)值为43500GHz，谐振频率温度系数tf为+3ppm/℃。注射成型工艺制备Ba2Ti9O20基介质谐振器通过以下工艺步骤实现：The main material formulation of this embodiment adopts a chemical formula: Ba 2 Ti 9 O 20 + 0.5 mol% ZrO 2 as a chemical composition, and compares the performance of the dielectric resonator prepared by the dry pressing method and the injection molding method, respectively, and the main material itself of the present embodiment is introduced. The electrical property relative permittivity εr was 40, the quality factor (Q×f) value was 43500 GHz, and the resonance frequency temperature coefficient tf was +3 ppm/°C. The Ba2Ti9O20 based dielectric resonator prepared by the injection molding process is realized by the following process steps:
(1)混合陶瓷粉体和有机粘结剂：将Ba2Ti9O20基陶瓷粉体和有机粘结剂混合均匀得到注射成型混合料，混料中不同成分的含量跟粉末的粒度、形貌、密度有关，所以不同的粉末其混合物配方不同；针对于Ba2Ti9O20基介质陶瓷，该注射成型混合料中，Ba2Ti9O20基陶瓷粉体的重量百分含量为78％，有机粘结剂的重量百分含量为22％；其中，该有机粘结剂由粘结剂、表面活性剂、低熔点有机 物和增塑剂组成，各组分重量百分含量为：粘结剂80％；表面活性剂：5％；低熔点有机物：10％；增塑剂：5％；(1) Mixed ceramic powder and organic binder: Ba 2 Ti 9 O 20 based ceramic powder and organic binder are uniformly mixed to obtain an injection molding mixture, and the content of different components in the mixture is the same as the particle size and shape of the powder. Appearance and density are related, so different powders have different mixture formulations; for Ba 2 Ti 9 O 20 based dielectric ceramics, the Ba 2 Ti 9 O 20 based ceramic powder has a weight percentage of 78 in the injection molding mixture. %, the organic binder has a weight percentage of 22%; wherein the organic binder is composed of a binder, a surfactant, a low melting point organic substance and a plasticizer, and the weight percentage of each component is: 80% of the binder; surfactant: 5%; low melting point organic: 10%; plasticizer: 5%;
(2)注射成型：注射成型混合料在注射成型机上注射成型得到坯体，注射温度为180℃，注入模具后在2分钟内脱模得到成型坯体；(2) Injection molding: injection molding mixture is injection molded on an injection molding machine to obtain a green body, the injection temperature is 180 ° C, and the mold is released after being injected into the mold within 2 minutes;
(3)非极性溶剂萃取脱脂：将注射成型得到的坯体放入非极性溶剂中，溶解脱除部分有机粘结剂，非极性溶剂的温度在30℃，脱脂时间为24小时，非极性溶剂萃取脱脂后的坯体在烘箱中充分干燥。(3) Non-polar solvent extraction degreasing: the injection-molded body is placed in a non-polar solvent to dissolve and remove part of the organic binder. The temperature of the non-polar solvent is 30 ° C, and the degreasing time is 24 hours. The non-polar solvent extraction degreased body is sufficiently dried in an oven.
(4)热脱脂：将干燥后的坯体放入电加热炉内进行热脱脂，以脱除剩余的有机粘结剂，该实施例中，以0.5℃/min的升温速率升温至550℃，保温2小时。(4) Thermal degreasing: the dried body is placed in an electric heating furnace for thermal degreasing to remove the remaining organic binder. In this embodiment, the temperature is raised to 550 ° C at a heating rate of 0.5 ° C / min. Keep warm for 2 hours.
(5)烧结：热脱脂后的坯体进行烧结，烧结温度为1400℃，保温2小时，得到介质谐振器。(5) Sintering: The body after thermal degreasing was sintered, the sintering temperature was 1400 ° C, and the temperature was kept for 2 hours to obtain a dielectric resonator.
分别用干压和注射成型工艺制备60个介质谐振器，样品如图3所示，从图3中可以看出注射成型与干压成型法制备的相比，晶粒尺寸更加均匀，颗粒尺寸更小，这对于Ba2Ti9O20基介质谐振器产品最终的性能和稳定性影响呈正相关关系。同时对样品的性能进行了测试，性能如表1：60 dielectric resonators were prepared by dry pressing and injection molding respectively. The sample is shown in Fig. 3. It can be seen from Fig. 3 that the injection molding is more uniform in grain size and the particle size is better than that prepared by dry pressing. Small, this is positively correlated with the final performance and stability of the Ba 2 Ti 9 O 20 based dielectric resonator product. At the same time, the performance of the sample was tested. The performance is shown in Table 1:
表1：注射成型和干压成型制备介质谐振器的性能参数对照Table 1: Comparison of performance parameters of dielectric resonators prepared by injection molding and dry compression molding
Figure PCTCN2015099947-appb-000001
Figure PCTCN2015099947-appb-000001
从表1可以看出注射成型制备的介质谐振器比传统干压法制备的性能更优，且性能稳定。It can be seen from Table 1 that the dielectric resonator prepared by injection molding has better performance and stable performance than the conventional dry pressing method.
实施例二Embodiment 2
本实施例主材料配方采用化学式：Ba2Ti9O20+1mol％ZrO2为化学组成，分别比较干压法和注射成型法制备的介质谐振器的性能，本实施例主材料本身的介电性能相对介电常数εr为39，品质因数(Q×f)值为50070GHz，谐振频率温度系数τf为-5ppm/℃。干压法主要通过造粒、压制成型后，进行烧结得到介质谐振器，工艺简单。注射成型工艺制备Ba2Ti9O20基介质谐振器通过以下工艺步骤实现： The main material formulation of this embodiment adopts a chemical formula: Ba 2 Ti 9 O 20 +1 mol% ZrO 2 as a chemical composition, and compares the performance of the dielectric resonator prepared by the dry pressing method and the injection molding method, respectively, and the dielectric of the main material itself in this embodiment The performance relative permittivity ε r was 39, the quality factor (Q × f) value was 50070 GHz, and the resonance frequency temperature coefficient τ f was -5 ppm / ° C. The dry pressing method mainly obtains a dielectric resonator by granulation, press molding, and sintering, and the process is simple. The Ba 2 Ti 9 O 20 based dielectric resonator prepared by the injection molding process is realized by the following process steps:
(1)混合陶瓷粉体和有机粘结剂：该实施例的注射成型混合料中，Ba2Ti9O20基陶瓷粉体的重量百分含量为75％，有机粘结剂的重量百分含量为25％；有机粘结剂中各组分重量百分含量为粘结剂80％；表面活性剂5％；低熔点有机物10％；增塑剂5％。(1) Mixed ceramic powder and organic binder: In the injection molding mixture of this embodiment, the Ba 2 Ti 9 O 20 -based ceramic powder has a weight percentage of 75%, and the weight percentage of the organic binder The content is 25%; the weight percentage of each component in the organic binder is 80% of the binder; 5% of the surfactant; 10% of the low melting organic substance; 5% of the plasticizer.
(2)注射成型：注射成型混合料在注射成型机上注射成型得到坯体，注射温度为180℃，注入模具后在2分钟内脱模得到成型坯体。(2) Injection molding: The injection molding mixture was injection molded on an injection molding machine to obtain a green body, and the injection temperature was 180 ° C. After injection into the mold, the molded body was released in 2 minutes.
(3)非极性溶剂萃取脱脂：将注射成型得到的坯体放入非极性溶剂中，溶解脱除部分有机粘结剂，非极性溶剂的温度为30℃，脱脂时间为24小时，非极性溶剂萃取脱脂后的坯体在烘箱中进行干燥。(3) Non-polar solvent extraction degreasing: the injection-molded body is placed in a non-polar solvent to dissolve and remove part of the organic binder. The temperature of the non-polar solvent is 30 ° C, and the degreasing time is 24 hours. The non-polar solvent extraction degreased body is dried in an oven.
(4)热脱脂：将干燥后的坯体放入电加热炉内进行热脱脂，以脱除剩余的有机粘结剂，该实施例中，以0.5℃/min的升温速率升温至550℃，保温2小时。(4) Thermal degreasing: the dried body is placed in an electric heating furnace for thermal degreasing to remove the remaining organic binder. In this embodiment, the temperature is raised to 550 ° C at a heating rate of 0.5 ° C / min. Keep warm for 2 hours.
(5)烧结：热脱脂后的坯体进行烧结，烧结温度为1400℃，保温2小时，得到介质谐振器。(5) Sintering: The body after thermal degreasing was sintered, the sintering temperature was 1400 ° C, and the temperature was kept for 2 hours to obtain a dielectric resonator.
分别用干压和注射成型工艺制备60个介质谐振器，并对样品的性能进行了测试，性能如表2：Sixty dielectric resonators were prepared by dry pressing and injection molding, and the performance of the samples was tested. The performance is shown in Table 2:
表2：注射成型和干压成型制备介质谐振器的性能参数对照Table 2: Comparison of performance parameters of dielectric resonators prepared by injection molding and dry compression molding
Figure PCTCN2015099947-appb-000002
Figure PCTCN2015099947-appb-000002
实施例三Embodiment 3
本实施例主材料配方采用化学式：Ba2Ti9O20+2mol％ZrO2为化学组成，分别比较干压法和注射成型法制备的介质谐振器的性能，本实施例主材料本身的介电性能相对介电常数εr为40，品质因数(Q×f)值为56000GHz，谐振频率温度系数τf为+2ppm/℃。干压法主要通过造粒、压制成型后，进行烧结得到介质谐振器，工艺简单。注射成型工艺制备Ba2Ti9O20基介质谐振器通过以下工艺步骤实现：The main material formulation of this embodiment adopts a chemical formula: Ba 2 Ti 9 O 20 + 2 mol% ZrO 2 as a chemical composition, and compares the performance of the dielectric resonator prepared by the dry pressing method and the injection molding method, respectively, and the dielectric of the main material itself in this embodiment The performance relative permittivity ε r is 40, the quality factor (Q × f) value is 56000 GHz, and the resonance frequency temperature coefficient τ f is +2 ppm / ° C. The dry pressing method mainly obtains a dielectric resonator by granulation, press molding, and sintering, and the process is simple. The Ba 2 Ti 9 O 20 based dielectric resonator prepared by the injection molding process is realized by the following process steps:
(1)混合陶瓷粉体和有机粘结剂：该实施例的注射成型混合料中，Ba2Ti9O20基陶瓷粉体的重量百分含量为75％，有机粘结剂的重量百分含量为25％；有机 粘结剂中各组分重量百分含量为粘结剂80％；表面活性剂5％；低熔点有机物10％；增塑剂5％。(1) Mixed ceramic powder and organic binder: In the injection molding mixture of this embodiment, the Ba 2 Ti 9 O 20 -based ceramic powder has a weight percentage of 75%, and the weight percentage of the organic binder The content is 25%; the weight percentage of each component in the organic binder is 80% of the binder; 5% of the surfactant; 10% of the low melting organic substance; 5% of the plasticizer.
(2)注射成型：注射成型混合料在注射成型机上注射成型得到坯体，注射温度为180℃，注入模具后在2分钟内脱模得到成型坯体。(2) Injection molding: The injection molding mixture was injection molded on an injection molding machine to obtain a green body, and the injection temperature was 180 ° C. After injection into the mold, the molded body was released in 2 minutes.
(3)非极性溶剂萃取脱脂：将注射成型得到的坯体放入非极性溶剂中，溶解脱除部分有机粘结剂，非极性溶剂的温度为30℃，脱脂时间为24小时，非极性溶剂萃取脱脂后的坯体在烘箱中进行干燥。(3) Non-polar solvent extraction degreasing: the injection-molded body is placed in a non-polar solvent to dissolve and remove part of the organic binder. The temperature of the non-polar solvent is 30 ° C, and the degreasing time is 24 hours. The non-polar solvent extraction degreased body is dried in an oven.
(4)热脱脂：将干燥后的坯体放入电加热炉内进行热脱脂，以脱除剩余的有机粘结剂，该实施例中，以0.5℃/min的升温速率升温至550℃，保温2小时。(4) Thermal degreasing: the dried body is placed in an electric heating furnace for thermal degreasing to remove the remaining organic binder. In this embodiment, the temperature is raised to 550 ° C at a heating rate of 0.5 ° C / min. Keep warm for 2 hours.
(5)烧结：热脱脂后的坯体进行烧结，烧结温度为1400℃，保温4小时，得到介质谐振器。(5) Sintering: The body after thermal degreasing was sintered, the sintering temperature was 1400 ° C, and the temperature was kept for 4 hours to obtain a dielectric resonator.
分别用干压和注射成型工艺制备60个介质谐振器，并对样品的性能进行了测试，性能如表3：Sixty dielectric resonators were prepared by dry pressing and injection molding, and the performance of the samples was tested. The performance is shown in Table 3:
表3：注射成型和干压成型制备介质谐振器的性能参数对照Table 3: Comparison of performance parameters of dielectric resonators prepared by injection molding and dry compression molding
Figure PCTCN2015099947-appb-000003
Figure PCTCN2015099947-appb-000003
本发明提供的Ba2Ti9O20基微波介质陶瓷材料谐振器的制备方法，通过将Ba2Ti9O20基介质陶瓷注射成型，可以得到具有密度和尺寸分布均匀、烧结后尺寸精度高的谐振器，且材料成本低，制备工艺简单。与干压制备的谐振器相比，还具有高的品质因数Q×f值和性能稳定性。The preparation method of the Ba 2 Ti 9 O 20 based microwave dielectric ceramic material resonator provided by the invention can obtain the uniformity of density and size distribution and high dimensional accuracy after sintering by injection molding Ba 2 Ti 9 O 20 based dielectric ceramic. The resonator has a low material cost and a simple preparation process. It also has a high quality factor Q x f value and performance stability compared to dry pressed resonators.
另外，本发明实施例还提供一种谐振器和一种腔体滤波器，该谐振器由上述实施例所述的制备方法制得。从上述实施例中的对比数据可知，分别用干压法和注射成型方法制备Ba2Ti9O20基材料的介质谐振器，干压法制备的介质谐振器的Q值为3500～4200，频率为1.6G，而注射成型制备的介质谐振器Q值可以达到3900～4300，频率为1.6G。可以看出，本发明中的利用注射成型制备的Ba2Ti9O20基材料的介质谐振器Q值更高，且性能更为稳定。In addition, an embodiment of the present invention further provides a resonator and a cavity filter which are prepared by the preparation method described in the above embodiments. It can be seen from the comparative data in the above embodiments that the dielectric resonator of the Ba 2 Ti 9 O 20 -based material is prepared by the dry pressing method and the injection molding method, respectively, and the Q value of the dielectric resonator prepared by the dry pressing method is 3500 to 4200, and the frequency is It is 1.6G, and the dielectric resonator prepared by injection molding has a Q value of 3900 to 4300 and a frequency of 1.6G. It can be seen that the dielectric resonator of the Ba 2 Ti 9 O 20 based material prepared by injection molding in the present invention has a higher Q value and more stable performance.
腔体滤波器包括上述实施例中的谐振器，由该谐振器具有较高的品质因数Q×f值和较低的谐振频率温度系数(τf)等优点，使之制备得到的腔体滤 波器具有较佳的介电性能和稳定性。而关于腔体滤波器的其他部分的结构及参数的技术特征在本领域技术人员的理解范围内，此处不再赘述。The cavity filter includes the resonator in the above embodiment, and the cavity has a higher quality factor Q×f value and a lower temperature coefficient of resonance frequency (τf), so that the cavity filter prepared by the cavity filter is prepared. The wave device has better dielectric properties and stability. The technical features of the structure and parameters of other parts of the cavity filter are within the understanding of those skilled in the art, and are not described herein again.
请参阅图4，图4是本发明射频拉远设备一优选实施例的结构组成框图，该射频拉远设备包括但不限于以下结构单元：射频收发信机模块510、功放模块520以及腔体滤波器530。其中，射频收发信机模块510与功放模块520连接，功放模块520进一步与腔体滤波器530连接。Please refer to FIG. 4. FIG. 4 is a structural block diagram of a preferred embodiment of the radio remote device of the present invention. The radio remote device includes but is not limited to the following structural units: a radio frequency transceiver module 510, a power amplifier module 520, and a cavity filter. 530. The radio frequency transceiver module 510 is connected to the power amplifier module 520, and the power amplifier module 520 is further connected to the cavity filter 530.
射频拉远设备工作在下行时隙时，来自射频收发信机模块510的两个通道的发射信号通过功放模块520进入腔体滤波器530，腔体滤波器530对发射信号完成滤波，然后功率合成后发射到天线口；射频拉远设备工作在上行时隙时，从天线口接收到的信号通过腔体滤波器530滤波后进入功放模块520，在经功放模块520放大后输出给射频收发信机模块510对应的接收通道。When the radio remote device operates in the downlink time slot, the transmit signals from the two channels of the radio transceiver module 510 enter the cavity filter 530 through the power amplifier module 520, and the cavity filter 530 filters the transmit signal, and then the power is synthesized. After being transmitted to the antenna port, the RF remote device operates in the uplink time slot, and the signal received from the antenna port is filtered by the cavity filter 530 and then enters the power amplifier module 520, and is amplified by the power amplifier module 520 and output to the RF transceiver. The receiving channel corresponding to module 510.
进一步地，该射频拉远设备还可以包括电源模块540，该电源模块540用于对该射频拉远设备的各个模块供电。Further, the radio remote device may further include a power module 540, and the power module 540 is configured to supply power to each module of the radio remote device.
以上所述仅为本发明的部分实施例，并非因此限制本发明的保护范围，凡是利用本发明说明书及附图内容所作的等效装置或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。 The above description is only a part of the embodiments of the present invention, and is not intended to limit the scope of the present invention. Any equivalent device or equivalent process transformation made by using the description of the present invention and the contents of the drawings may be directly or indirectly applied to other related The technical field is equally included in the scope of patent protection of the present invention.

Claims (20)

  1. 一种Ba2Ti9O20基微波介质陶瓷材料的制备方法，其特征在于，所述制备方法包括：A method for preparing a Ba 2 Ti 9 O 20 based microwave dielectric ceramic material, characterized in that the preparation method comprises:
    制备混合料，所述混合料中至少包括Ba2Ti9O20基陶瓷粉体和有机粘结剂；Preparing a mixture comprising at least Ba 2 Ti 9 O 20 based ceramic powder and an organic binder;
    将所述混合料注射成型，得到坯体；Injection molding the mixture to obtain a green body;
    将所述胚体先后进行非极性溶剂萃取脱脂和热脱脂；The embryo body is subjected to non-polar solvent extraction degreasing and thermal degreasing;
    将热脱脂后的坯体进行烧结，以得到所述Ba2Ti9O20基微波介质陶瓷。The thermally degreased green body is sintered to obtain the Ba 2 Ti 9 O 20 based microwave dielectric ceramic.
  2. 根据权利要求1所述的制备方法，其特征在于，所述混合料中的Ba2Ti9O20基陶瓷粉体的重量百分含量为76～85％，所述有机粘结剂的重量百分含量为15～24％。The preparation method according to claim 1, wherein the Ba 2 Ti 9 O 20 -based ceramic powder in the mixture has a weight percentage of 76 to 85%, and the weight of the organic binder is 100%. The content of the fraction is 15 to 24%.
  3. 根据权利要求2所述的制备方法，其特征在于，所述Ba2Ti9O20基陶瓷粉体的配方化学式为Ba2Ti9O20+ax+by，其中x、y至少包括MoO3、MnO2、WO3、SnO2、B2O3、ZnO、Nb2O5、ZrO2、CaCO3、SrCO3、PbCO3中的一种或多种，0≤a，b≤0.20mol。The preparation method according to claim 2, wherein the Ba 2 Ti 9 O 20 -based ceramic powder has a formula of Ba 2 Ti 9 O 20 + ax + by, wherein x and y include at least MoO 3 , One or more of MnO 2 , WO 3 , SnO 2 , B 2 O 3 , ZnO, Nb 2 O 5 , ZrO 2 , CaCO 3 , SrCO 3 , and PbCO 3 , 0 ≤ a, b ≤ 0.20 mol.
  4. 根据权利要求1所述的制备方法，其特征在于，所述有机粘结剂包括粘结剂、表面活性剂、低熔点有机物以及增塑剂。The preparation method according to claim 1, wherein the organic binder comprises a binder, a surfactant, a low melting point organic substance, and a plasticizer.
  5. 根据权利要求1所述的制备方法，其特征在于，所述将混合料注射成型的步骤包括：The preparation method according to claim 1, wherein the step of injection molding the mixture comprises:
    将所述混合料在注射成型机中加热成粘稠性熔体；Heating the mixture into a viscous melt in an injection molding machine;
    将所述粘稠性熔体注入模具内，在模具内冷却后脱模得到坯体；The viscous melt is injected into the mold, and after being cooled in the mold, the mold is released to obtain a green body;
    其中，注射温度为170℃～200℃。Among them, the injection temperature is 170 ° C ~ 200 ° C.
  6. 根据权利要求1所述的制备方法，其特征在于，所述胚体的非极性溶剂萃取脱脂过程具体包括：The preparation method according to claim 1, wherein the non-polar solvent extraction degreasing process of the embryo body comprises:
    将注射成型得到的坯体放入非极性溶剂中，以溶解脱除部分有机粘结剂；The injection-molded body is placed in a non-polar solvent to dissolve and remove part of the organic binder;
    将非极性溶剂萃取脱脂后的坯体进行干燥。The non-polar solvent is extracted and the degreased body is dried.
  7. 根据权利要求6所述的制备方法，其特征在于，将经由非极性溶剂萃取脱脂并干燥的胚体继续进行热脱脂，以脱除胚体中剩余的有机粘结剂，所述热脱脂的过程为：将胚体以0.5～5℃/min的升温速率升温至550℃，然后保温2～3小时。The preparation method according to claim 6, wherein the degreased and dried embryo body is subjected to thermal degreasing by extracting the non-polar solvent to remove the remaining organic binder in the embryo body, the thermal degreasing The process is as follows: the embryo body is heated to 550 ° C at a heating rate of 0.5 to 5 ° C / min, and then kept for 2 to 3 hours.
  8. 根据权利要求1所述的制备方法，其特征在于，所述烧结的温度为 1200～1400℃，加热后保温2～6小时。The preparation method according to claim 1, wherein the sintering temperature is 1200 ~ 1400 ° C, heat for 2 to 6 hours.
  9. 根据权利要求6所述的制备方法，其特征在于，所述胚体非极性溶剂萃取脱脂过程中的非极性溶剂的温度为30～50℃，脱脂时间为12～36小时；脱脂后进行干燥的温度为50～70℃，干燥时间为4～12h。The preparation method according to claim 6, wherein the non-polar solvent in the non-polar solvent extraction and degreasing process has a temperature of 30 to 50 ° C and a degreasing time of 12 to 36 hours; The drying temperature is 50 to 70 ° C, and the drying time is 4 to 12 hours.
  10. 根据权利要求4所述的制备方法，其特征在于，所述有机粘结剂中各组分的重量百分含量为：粘结剂50～90％；表面活性剂1～5％；低熔点有机物2～11％以及增塑剂1～11％。The preparation method according to claim 4, wherein the weight percentage of each component in the organic binder is: 50 to 90% of the binder; 1 to 5% of the surfactant; and the low melting point organic substance 2 to 11% and plasticizer 1 to 11%.
  11. 根据权利要求10所述的制备方法，其特征在于，所述粘结剂至少包括石蜡、乙烯-乙酸乙烯脂共聚物、聚丙烯、无规聚丙烯、聚苯乙烯、聚甲基丙烯酸酯、乙烯丙烯酸乙酯共聚物中的一种或多种；所述表面活性剂至少包括硬脂酸、辛酸、微晶石蜡中的一种或多种；所述增塑剂至少包括邻苯二甲酸二丁酯、邻苯二甲酸二乙酯、邻苯二甲酸二辛脂中的一种或多种。The preparation method according to claim 10, wherein the binder comprises at least paraffin wax, ethylene-vinyl acetate copolymer, polypropylene, atactic polypropylene, polystyrene, polymethacrylate, ethylene. One or more of ethyl acrylate copolymers; the surfactant includes at least one or more of stearic acid, octanoic acid, and microcrystalline paraffin; and the plasticizer includes at least dibutyl phthalate One or more of an ester, diethyl phthalate, and dioctyl phthalate.
  12. 一种Ba2Ti9O20基微波介质陶瓷材料，其特征在于，所述微波介质陶瓷材料中包括重量百分含量为76～85％的Ba2Ti9O20基陶瓷粉体以及重量百分含量为15～24％的有机粘结剂。A Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material, characterized in that the microwave dielectric ceramic material comprises Ba 2 Ti 9 O 20 based ceramic powder in a weight percentage of 76-85% and a weight percentage The organic binder has a content of 15 to 24%.
  13. 根据权利要求12所述的微波介质陶瓷材料，其特征在于，所述Ba2Ti9O20基陶瓷粉体的配方化学式为Ba2Ti9O20+ax+by，其中x、y至少包括MoO3、MnO2、WO3、SnO2、B2O3、ZnO、Nb2O5、ZrO2、CaCO3、SrCO3、PbCO3中的一种或多种，0mol≤a，b≤0.20mol。The microwave dielectric ceramic material according to claim 12, wherein the Ba 2 Ti 9 O 20 -based ceramic powder has a formula of Ba 2 Ti 9 O 20 + ax + by, wherein x and y include at least MoO 3 , one or more of MnO 2 , WO 3 , SnO 2 , B 2 O 3 , ZnO, Nb 2 O 5 , ZrO 2 , CaCO 3 , SrCO 3 , PbCO 3 , 0 mol ≤ a, b ≤ 0.20 mol .
  14. 根据权利要求12所述的微波介质陶瓷材料，其特征在于，所述有机粘结剂包括粘结剂、表面活性剂、低熔点有机物以及增塑剂。The microwave dielectric ceramic material according to claim 12, wherein the organic binder comprises a binder, a surfactant, a low melting point organic, and a plasticizer.
  15. 根据权利要求14所述的微波介质陶瓷材料，其特征在于，所述有机粘结剂中各组分的重量百分含量为：粘结剂50～90％；表面活性剂1～5％；低熔点有机物2～11％以及增塑剂1～11％。The microwave dielectric ceramic material according to claim 14, wherein the weight percentage of each component in the organic binder is: 50 to 90% of the binder; 1 to 5% of the surfactant; The organic matter at the melting point is 2 to 11% and the plasticizer is 1 to 11%.
  16. 根据权利要求14所述的微波介质陶瓷材料，其特征在于，所述粘结剂至少包括石蜡、乙烯-乙酸乙烯脂共聚物、聚丙烯、无规聚丙烯、聚苯乙烯、聚甲基丙烯酸酯、乙烯丙烯酸乙酯共聚物中的一种或多种；所述表面活性剂至少包括硬脂酸、辛酸、微晶石蜡中的一种或多种；所述增塑剂至少包括邻苯二甲酸二丁酯、邻苯二甲酸二乙酯、邻苯二甲酸二辛脂中的一种或多种。The microwave dielectric ceramic material according to claim 14, wherein said binder comprises at least paraffin wax, ethylene-vinyl acetate copolymer, polypropylene, atactic polypropylene, polystyrene, polymethacrylate And one or more of ethylene ethyl acrylate copolymer; the surfactant comprises at least one or more of stearic acid, octanoic acid, and microcrystalline paraffin; and the plasticizer comprises at least phthalic acid One or more of dibutyl ester, diethyl phthalate, and dioctyl phthalate.
  17. 一种谐振器，其特征在于，所述谐振器由权利要求1-11任一项所述的制备方法制得。 A resonator characterized in that the resonator is produced by the preparation method according to any one of claims 1-11.
  18. 一种腔体滤波器，其特征在于，所述腔体滤波器包括腔体、盖板以及权利要求17所述的谐振器，所述盖板封盖所述腔体以形成谐振腔，所述谐振器安装在所述腔体内。A cavity filter, comprising: a cavity, a cover plate, and the resonator of claim 17, the cover plate covering the cavity to form a resonant cavity, A resonator is mounted within the cavity.
  19. 一种射频拉远设备，其特征在于，所述射频拉远设备包括：射频收发信机模块、功放模块以及权利要求18所述的腔体滤波器，所述射频收发信机模块与所述功放模块连接，所述功放模块与所述腔体滤波器连接。A radio remote device, the radio remote device comprising: a radio frequency transceiver module, a power amplifier module, and the cavity filter of claim 18, the radio frequency transceiver module and the power amplifier A module is connected, and the power amplifier module is connected to the cavity filter.
  20. 一种Ba2Ti9O20基微波介质陶瓷材料的配方，其特征在于，包括以下重量百分含量的组分：A formulation of a Ba 2 Ti 9 O 20 -based microwave dielectric ceramic material characterized by comprising the following components by weight:
    Ba2Ti9O20基陶瓷粉体76～85％；Ba 2 Ti 9 O 20 based ceramic powder 76-85%;
    有机粘结剂15～24％。 The organic binder is 15 to 24%.
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