CN111470861B - Microwave dielectric ceramic material and method for preparing microwave ceramic filter device by using same - Google Patents
Microwave dielectric ceramic material and method for preparing microwave ceramic filter device by using same Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 44
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 44
- 239000002002 slurry Substances 0.000 claims description 39
- 239000012153 distilled water Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 24
- 238000010304 firing Methods 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims 3
- 238000005245 sintering Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000003780 insertion Methods 0.000 abstract description 2
- 230000037431 insertion Effects 0.000 abstract description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- 238000003825 pressing Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 229910002971 CaTiO3 Inorganic materials 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910017682 MgTi Inorganic materials 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
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- H01P1/20—Frequency-selective devices, e.g. filters
- H01P1/2002—Dielectric waveguide filters
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Abstract
The invention discloses a microwave dielectric ceramic material and a method for preparing a microwave ceramic filter device by using the same, wherein the microwave dielectric ceramic material is prepared by mixing 100 wt% of microwave dielectric ceramic base powder and 0.6-2 wt% of low-temperature sintering aid, and the chemical composition formula of the microwave dielectric ceramic base powder is as follows: 95Mg1.15TiO3‑5CaTiO3The low-temperature sintering aid is ZnO2A composition for coating rare earth oxide. The microwave dielectric ceramic material prepared by the invention has good microwave performance, greatly reduces the sintering temperature, shortens the sintering time, and can be used for preparing a microwave ceramic filter with the advantages of high stop band, low insertion loss, wide frequency band and low time delay, thereby having wide market application prospect.
Description
Technical Field
The invention belongs to inorganic non-metallic materials, and particularly relates to a microwave dielectric ceramic material and a method for preparing a microwave ceramic filter device by using the same.
Background
Microwave ceramic filter devices, such as ZnO filters, are currently made using small amounts of additives added to the filter during microwave ceramic production2And CeO2、Pr6011、Nd2O3、Sm2O3Or ZnO2And Pr6011Or ZnO2And Sm2O3The composite additive of (1); or low melting point oxides, glasses, etc. Such as MgTiO3-CaTiO3Although microwave ceramics have the characteristics of moderate dielectric constant and good temperature stability, and can manufacture a series of ceramics with different frequency temperature coefficients by adjusting components, the ceramics have the defects of low Q value and high firing temperature, and can only be used in occasions with low requirements. Such as new mobile communication equipment, 5G universal serial busThe establishment of a base station requires a microwave ceramic with a higher Q value.
LaAlO3-CaTiO3The microwave ceramic has high Q value (Q reaches 6500 and 10GHz), and because the firing temperature is high (1600 ℃), a large amount of rare earth is used, and the price is very expensive. The Q value of the microwave ceramics is always difficult to improve in the production of the microwave ceramics, and particularly, the microwave ceramics is sintered at a lower temperature. Such as MgTiO at present3-CaTiO3The sintering Q of the microwave ceramic at 1375 ℃ only reaches 5900 reported (10GHz), so that a microwave ceramic with a dielectric constant of 20.2-20.8 and a frequency temperature coefficient absolute value of 12 multiplied by 10 is developed-6MgTiO with higher Q value below/° C3-CaTiO3The microwave ceramic has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a microwave dielectric ceramic material with excellent performance, simple process and low cost and a method for preparing a microwave ceramic filter device by using the material.
The invention is realized by the following technical scheme: a microwave dielectric ceramic material is characterized in that: the microwave dielectric ceramic material is prepared by mixing 100 wt% of microwave dielectric ceramic base powder and 0.6-2 wt% of low-temperature sintering aid, and the chemical composition formula of the microwave dielectric ceramic powder is as follows: 95Mg1.15TiO3-5CaTiO3The low-temperature sintering aid is ZnO2A composition for coating rare earth oxide.
The low temperature sintering aid is comprised of one or more compositions.
The rare earth oxide is CeO2、Pr6011、Nd2O3、Sm2O3One kind of (1).
The preparation steps of the low-temperature sintering aid are as follows:
the method comprises the following steps: ball milling analytically pure rare earth oxide for 6 hours to obtain d50Particles of 0.8 um;
step two: weighing the rare earth oxide particles obtained in the step one and Zn (NO) according to the molar ratio of 1.16:13)26H2O powder;
step three: according to the dosage of the rare earth oxide in the step two, measuring distilled water according to the molar ratio of 1:114, pouring the distilled water into a container containing rare earth oxide particles, and dispersing for 30 minutes by using an ultrasonic cleaner to obtain a solution A;
step four: according to step two Zn (NO)3)26H2Measuring the amount of O, measuring distilled water according to the molar ratio of 1:130, and pouring the distilled water into the container containing Zn (NO)3)26H2In a container of O powder, and then stirred with a glass rod for several minutes, Zn (NO)3)26H2Completely dissolving the O powder to obtain a B solution;
step five: putting the magneton into the solution A, putting the solution A into a container with a water bath temperature of 62-82 ℃, putting the container on a magnetic stirrer platform for stirring, and pouring the solution B into the solution A to obtain a mixed solution;
step six: dropwise adding ammonia water into the mixed solution, adjusting the pH value to 7, controlling the reaction time to be 25-60 minutes, standing for 28 hours after the reaction is finished, and then performing suction filtration, multiple washing and air drying to obtain a precipitate;
step seven: and putting the precipitate into a crucible for calcining, wherein the calcining temperature is 680 ℃, keeping the temperature for 30 minutes, and grinding the calcined product to obtain the low-temperature sintering aid.
The preparation steps of the basic powder material are as follows:
the method comprises the following steps: in proportion of 95Mg1.15TiO3-5CaTiO3Weighing MgO and CaCO3And TiO2Then preparing slurry according to the ratio of the material to the ball to the water =1:2: 2;
step two: and (4) sieving, drying, dehydrating and calcining the slurry prepared in the step one to synthesize the microwave dielectric ceramic base powder.
D of MgO in the first step501.2-1.8 um; the firing system of the calcining procedure in the second step is as follows: increasing the temperature from room temperature to 400 ℃ in 180min, increasing the temperature from 400 ℃ to 900 ℃ in 180min, increasing the temperature from 900 ℃ to 1080 ℃ in 180min, and preserving the heat at 1080 ℃ for 240 min.
The method for preparing the microwave ceramic filter device by using the microwave dielectric ceramic material is characterized by comprising the following steps of:
the method comprises the following steps: ball-milling a microwave dielectric ceramic material according to the ratio of balls to water =1:2:1 to obtain slurry, and drying to obtain a formula material;
step two: ball milling is carried out for 12 hours according to the formula materials, the binder and the water are =1: 0.6-1.8: 1.2 to obtain slurry, the slurry is sieved and stirred at a low speed and then is sent into a drying tower to obtain the product d50Processing materials which are 0.15mm spherical, and then pressing the processing materials into a green body of the microwave ceramic filter device by using a press;
step three: placing the microwave ceramic filter device blank in a kiln, firing at 1340 ℃, preserving heat for 4 hours, and naturally cooling to obtain a microwave ceramic filter device;
step four: and spraying or dipping a layer of electrode on the microwave ceramic filter ceramic part, firing at 900 ℃, keeping the temperature for 0.5 hour, naturally cooling, and manufacturing input and output end electrodes to obtain the microwave ceramic filter device.
The density of the microwave ceramic filter device blank in the second step is 2.5g/cm3(ii) a The binder is a mixed solution of polyvinyl alcohol and polyethylene glycol with the concentration of 10%, wherein the molar ratio of the polyvinyl alcohol to the polyethylene glycol is 10: 0.3.
The thickness of the electrode in the fourth step is 10 um.
The microwave dielectric ceramic material has a Q value of 6300-7200 (10GHz), a dielectric constant of 20.2-20.8, and a frequency temperature coefficient absolute value of 12 x 10-6Below/° c.
The invention adopts non-stoichiometric ratio Mg1.15TiO3The microwave dielectric ceramic material with good performance is obtained by the traditional solid phase ceramic preparation process, because MgTiO is used as a main crystal phase component and the micron particles coated by the nano particles are used as a low-temperature sintering aid3The excessive 0.15 mol of medium MgO not only effectively inhibits MgTi with low Q value2O5The growth of the phase also reduces the sintering temperature; the addition of the low-temperature sintering aid with the nano particles wrapping the micro particles improves the microwave performance and reduces the sintering temperature; meanwhile, the microwave dielectric ceramic material can be used for preparing a high-stop band, low insertion loss and wide bandThe microwave ceramic filter has the advantages of short section and low time delay, thereby having wide market application prospect.
Detailed Description
Example 1
（1）95Mg1.15TiO3-5CaTiO3-1.4((Sm2O3)@ZnO2) Preparation of microwave dielectric ceramic material
A microwave dielectric ceramic material is prepared from 95Mg (100 wt.%)1.15TiO3-5CaTiO3And 1.4 wt.% ((Sm)2O3)@ZnO2) Mixing to obtain the final product.
The low-temperature sintering aid ((Sm)2O3)@ZnO2) The preparation steps are as follows:
the method comprises the following steps: will analyze pure Sm2O3Ball milling for 6 hours to obtain d50Particles of 0.8 um;
step two: weighing Sm obtained in the step one according to the molar ratio of 1.16:12O3Particles and Zn (NO)3)26H2O powder;
step three: according to the second step Sm2O3The amount of the components is measured according to the molar ratio of 1:114, distilled water is poured into the container with Sm2O3Dispersing the particles in a container by using an ultrasonic cleaner for 30 minutes to obtain a solution A;
step four: according to step two Zn (NO)3)26H2Measuring the amount of O, measuring distilled water according to the molar ratio of 1:130, and pouring the distilled water into the container containing Zn (NO)3)26H2In a container of O powder, and then stirred with a glass rod for several minutes, Zn (NO)3)26H2Completely dissolving the O powder to obtain a B solution;
step five: adding magnetons into the solution A, then placing the solution A into a container with the water bath temperature of 62 ℃, placing the container on a magnetic stirrer platform for stirring, and then pouring the solution B into the solution A to obtain a mixed solution;
step six: dropwise adding ammonia water into the mixed solution, adjusting the pH value to 7, controlling the reaction time to be 26 minutes, standing for 28 hours after the reaction is finished, and then performing suction filtration, multiple washing and air drying to obtain a precipitate;
step seven: and putting the precipitate into a crucible for calcining, wherein the calcining temperature is 680 ℃, keeping the temperature for 30 minutes, and grinding the calcined product to obtain the low-temperature sintering aid.
The preparation steps of the basic powder material are as follows:
the method comprises the following steps: in proportion of 95Mg1.15TiO3-5CaTiO3Weighing MgO (d)501.2-1.8 um), CaCO3And TiO2Then preparing slurry according to the ratio of the material to the ball to the water =1:2: 2;
step two: the slurry prepared in the step one is screened, dried, dehydrated and calcined to synthesize microwave dielectric ceramic base powder;
d of MgO in the first step50Is 1.2 um; the firing system of the calcining procedure in the second step is as follows: increasing the temperature from room temperature to 400 ℃ in 180min, increasing the temperature from 400 ℃ to 900 ℃ in 180min, increasing the temperature from 900 ℃ to 1080 ℃ in 180min, and preserving the heat at 1080 ℃ for 240 min.
(2) Method for preparing microwave ceramic filter device by using microwave dielectric ceramic material
The method comprises the following steps: mixing 95Mg1.15TiO3-5CaTiO3-1.4((Sm2O3)@ZnO2) Ball milling is carried out according to the ratio of balls to water =1:2:1 to obtain slurry, and the slurry is dried to obtain a formula material;
step two: ball milling is carried out for 12 hours according to the formula materials, the binder and the water are =1:0.8:1.2 to obtain slurry, the slurry is sieved and stirred at a low speed and then is sent into a drying tower to obtain the product d50Processing materials which are 0.15mm spherical, and then pressing the processing materials into a green body of the microwave ceramic filter device by using a press;
step three: placing the microwave ceramic filter device blank in a kiln, firing at 1340 ℃, preserving heat for 4 hours, and naturally cooling to obtain a microwave ceramic filter device;
step four: and spraying or dipping a layer of electrode on the microwave ceramic filter ceramic part, firing at 900 ℃, keeping the temperature for 0.5 hour, naturally cooling, and manufacturing input and output end electrodes to obtain the microwave ceramic filter device.
The density of the microwave ceramic filter device blank in the second step is 2.5g/cm3(ii) a The binder is a mixed solution of polyvinyl alcohol and polyethylene glycol with the concentration of 10%, wherein the molar ratio of the polyvinyl alcohol to the polyethylene glycol is 10: 0.3.
The thickness of the electrode in the fourth step is 10 um.
The microwave dielectric ceramic material has a Q value of 6500(10GHz), a dielectric constant of 20.6 and a frequency temperature coefficient absolute value of 10 multiplied by 10-6/℃。
Example 2
（1）95Mg1.15TiO3-5CaTiO3-1.2((Pr6011)@ZnO2) Preparation of microwave dielectric ceramic material
A microwave dielectric ceramic material is prepared from 95Mg (100 wt.%)1.15TiO3-5CaTiO3And 1.2 wt.% ((Pr)6011)@ZnO2) Mixing to obtain the final product.
The low-temperature sintering aid ((Pr)6011)@ZnO2) The preparation steps are as follows:
the method comprises the following steps: will analytically pure Pr6011Ball milling for 6 hours to obtain d50Particles of 0.8 um;
step two: weighing the Pr obtained in the step one according to the molar ratio of 1.16:16011Particles and Zn (NO)3)26H2O powder;
step three: according to step II Pr6011The amount of the raw materials is measured according to the molar ratio of 1:114, distilled water is poured into the container containing Pr6011Dispersing the particles in a container by using an ultrasonic cleaner for 30 minutes to obtain a solution A;
step four: according to step two Zn (NO)3)26H2Measuring the amount of O, measuring distilled water according to the molar ratio of 1:130, and pouring the distilled water into the container containing Zn (NO)3)26H2In a container of O powder, and then stirred with a glass rod for several minutes, Zn (NO)3)26H2Completely dissolving the O powder to obtain a B solution;
step five: adding magnetons into the solution A, then placing the solution A into a container with the water bath temperature of 70 ℃, placing the container on a magnetic stirrer platform for stirring, and then pouring the solution B into the solution A to obtain a mixed solution;
step six: dropwise adding ammonia water into the mixed solution, adjusting the pH value to 7, controlling the reaction time to be 35 minutes, standing for 28 hours after the reaction is finished, and then performing suction filtration, multiple washing and air drying to obtain a precipitate;
step seven: and putting the precipitate into a crucible for calcining, wherein the calcining temperature is 680 ℃, keeping the temperature for 30 minutes, and grinding the calcined product to obtain the low-temperature sintering aid.
The preparation steps of the basic powder material are as follows:
the method comprises the following steps: in proportion of 95Mg1.15TiO3-5CaTiO3Weighing MgO (d)501.2-1.8 um), CaCO3And TiO2Then preparing slurry according to the ratio of the material to the ball to the water =1:2: 2;
step two: the slurry prepared in the step one is screened, dried, dehydrated and calcined to synthesize microwave dielectric ceramic base powder;
d of MgO in the first step50Is 1.4 um; the firing system of the calcining procedure in the second step is as follows: increasing the temperature from room temperature to 400 ℃ in 180min, increasing the temperature from 400 ℃ to 900 ℃ in 180min, increasing the temperature from 900 ℃ to 1080 ℃ in 180min, and preserving the heat at 1080 ℃ for 240 min.
(2) Method for preparing microwave ceramic filter device by using microwave dielectric ceramic material
The method comprises the following steps: mixing 95Mg1.15TiO3-5CaTiO3-1.2((Pr6011)@ZnO2) Ball milling is carried out according to the ratio of balls to water =1:2:1 to obtain slurry, and the slurry is dried to obtain a formula material;
step two: ball milling is carried out for 12 hours according to the formula materials, the binder and the water are =1:1:1.2 to obtain slurry, the slurry is sieved and stirred at a low speed and then is sent into a drying tower to obtain the product d50Processing materials which are 0.15mm spherical, and then pressing the processing materials into a green body of the microwave ceramic filter device by using a press;
step three: placing the microwave ceramic filter device blank in a kiln, firing at 1340 ℃, preserving heat for 4 hours, and naturally cooling to obtain a microwave ceramic filter device;
step four: and spraying or dipping a layer of electrode on the microwave ceramic filter ceramic part, firing at 900 ℃, keeping the temperature for 0.5 hour, naturally cooling, and manufacturing input and output end electrodes to obtain the microwave ceramic filter device.
The density of the microwave ceramic filter device blank in the second step is 2.5g/cm3(ii) a The binder is a mixed solution of polyvinyl alcohol and polyethylene glycol with the concentration of 10%, wherein the molar ratio of the polyvinyl alcohol to the polyethylene glycol is 10: 0.3.
The thickness of the electrode in the fourth step is 10 um.
The microwave dielectric ceramic material has a Q value of 6800(10GHz), a dielectric constant of 20.4 and a frequency temperature coefficient absolute value of 5 multiplied by 10-6/℃。
Example 3
（1）95Mg1.15TiO3-5CaTiO3-1.6((Nd2O3)@ZnO2) Preparation of microwave dielectric ceramic material
A microwave dielectric ceramic material is prepared from 95Mg (100 wt.%)1.15TiO3-5CaTiO3And 1.6 wt.% ((Nd)2O3)@ZnO2) Mixing to obtain the final product.
The low-temperature sintering aid ((Nd)2O3)@ZnO2) The preparation steps are as follows:
the method comprises the following steps: will analytically pure Nd2O3Ball milling for 6 hours to obtain d50Particles of 0.8 um;
step two: weighing Nd obtained in the first step according to a molar ratio of 1.16:12O3Particles and Zn (NO)3)26H2O powder;
step three: according to step di Nd2O3The amount of the Nd-containing compound is measured according to the molar ratio of 1:114, and then the distilled water is poured into the Nd-containing compound2O3Dispersing the particles in a container by using an ultrasonic cleaner for 30 minutes to obtain a solution A;
step four: according to step two Zn (NO)3)26H2Measuring the amount of O, measuring distilled water according to the molar ratio of 1:130, and pouring the distilled water into the container containing Zn (NO)3)26H2In a container of O powder, and then stirred with a glass rod for several minutes, Zn (NO)3)26H2Completely dissolving the O powder to obtain a B solution;
step five: adding magnetons into the solution A, then placing the solution A into a container with the water bath temperature of 75 ℃, placing the container on a magnetic stirrer platform for stirring, and then pouring the solution B into the solution A to obtain a mixed solution;
step six: dropwise adding ammonia water into the mixed solution, adjusting the pH value to 7, controlling the reaction time to be 40 minutes, standing for 28 hours after the reaction is finished, and then performing suction filtration, multiple washing and air drying to obtain a precipitate;
step seven: and putting the precipitate into a crucible for calcining, wherein the calcining temperature is 680 ℃, keeping the temperature for 30 minutes, and grinding the calcined product to obtain the low-temperature sintering aid.
The preparation steps of the basic powder material are as follows:
the method comprises the following steps: in proportion of 95Mg1.15TiO3-5CaTiO3Weighing MgO (d)501.2-1.8 um), CaCO3And TiO2Then preparing slurry according to the ratio of the material to the ball to the water =1:2: 2;
step two: the slurry prepared in the step one is screened, dried, dehydrated and calcined to synthesize microwave dielectric ceramic base powder;
d of MgO in the first step50Is 1.5 um; the firing system of the calcining procedure in the second step is as follows: increasing the temperature from room temperature to 400 ℃ in 180min, increasing the temperature from 400 ℃ to 900 ℃ in 180min, increasing the temperature from 900 ℃ to 1080 ℃ in 180min, and preserving the heat at 1080 ℃ for 240 min.
(2) Method for preparing microwave ceramic filter device by using microwave dielectric ceramic material
The method comprises the following steps: mixing 95Mg1.15TiO3-5CaTiO3-1.6((Nd2O3)@ZnO2) Ball milling is carried out according to the ratio of balls to water =1:2:1 to obtain slurry, and the slurry is dried to obtain a formula material;
step two: the formula materials comprise the following components:ball milling with water =1:1.2:1.2 for 12 hours to obtain slurry, sieving, slowly stirring, and feeding into a drying tower to obtain the product d50Processing materials which are 0.15mm spherical, and then pressing the processing materials into a green body of the microwave ceramic filter device by using a press;
step three: placing the microwave ceramic filter device blank in a kiln, firing at 1340 ℃, preserving heat for 4 hours, and naturally cooling to obtain a microwave ceramic filter device;
step four: and spraying or dipping a layer of electrode on the microwave ceramic filter ceramic part, firing at 900 ℃, keeping the temperature for 0.5 hour, naturally cooling, and manufacturing input and output end electrodes to obtain the microwave ceramic filter device.
The density of the microwave ceramic filter device blank in the second step is 2.5g/cm3(ii) a The binder is a mixed solution of polyvinyl alcohol and polyethylene glycol with the concentration of 10%, wherein the molar ratio of the polyvinyl alcohol to the polyethylene glycol is 10: 0.3.
The thickness of the electrode in the fourth step is 10 um.
The microwave dielectric ceramic material has a Q value of 7100(10GHz), a dielectric constant of 20.7 and a frequency temperature coefficient absolute value of 6 multiplied by 10-6/℃。
Example 4
（1）95Mg1.15TiO3-5CaTiO3-1.5((CeO2)@ZnO2) Preparation of microwave dielectric ceramic material
A microwave dielectric ceramic material is prepared from 95Mg (100 wt.%)1.15TiO3-5CaTiO3And 1.5 wt.% ((CeO)2)@ZnO2) Mixing to obtain the final product.
The low-temperature sintering aid ((CeO)2)@ZnO2) The preparation steps are as follows:
the method comprises the following steps: will analytically pure CeO2Ball milling for 6 hours to obtain d50Particles of 0.8 um;
step two: the CeO obtained in the first step is weighed according to the molar ratio of 1.16:12Particles and Zn (NO)3)26H2O powder;
step three: according to the step II CeO2The amount of the (B) to be used,measuring distilled water according to the molar ratio of 1:114, pouring the distilled water into the CeO2Dispersing the particles in a container by using an ultrasonic cleaner for 30 minutes to obtain a solution A;
step four: according to step two Zn (NO)3)26H2Measuring the amount of O, measuring distilled water according to the molar ratio of 1:130, and pouring the distilled water into the container containing Zn (NO)3)26H2In a container of O powder, and then stirred with a glass rod for several minutes, Zn (NO)3)26H2Completely dissolving the O powder to obtain a B solution;
step five: adding magnetons into the solution A, then placing the solution A into a container with the water bath temperature of 80 ℃, placing the container on a magnetic stirrer platform for stirring, and then pouring the solution B into the solution A to obtain a mixed solution;
step six: dropwise adding ammonia water into the mixed solution, adjusting the pH value to 7, controlling the reaction time to be 45 minutes, standing for 28 hours after the reaction is finished, and then performing suction filtration, multiple washing and air drying to obtain a precipitate;
step seven: and putting the precipitate into a crucible for calcining, wherein the calcining temperature is 680 ℃, keeping the temperature for 30 minutes, and grinding the calcined product to obtain the low-temperature sintering aid.
The preparation steps of the basic powder material are as follows:
the method comprises the following steps: in proportion of 95Mg1.15TiO3-5CaTiO3Weighing MgO (d)501.2-1.8 um), CaCO3And TiO2Then preparing slurry according to the ratio of the material to the ball to the water =1:2: 2;
step two: the slurry prepared in the step one is screened, dried, dehydrated and calcined to synthesize microwave dielectric ceramic base powder;
d of MgO in the first step50Is 1.6 um; the firing system of the calcining procedure in the second step is as follows: increasing the temperature from room temperature to 400 ℃ in 180min, increasing the temperature from 400 ℃ to 900 ℃ in 180min, increasing the temperature from 900 ℃ to 1080 ℃ in 180min, and preserving the heat at 1080 ℃ for 240 min.
(2) Method for preparing microwave ceramic filter device by using microwave dielectric ceramic material
The method comprises the following steps: mixing 95Mg1.15TiO3-5CaTiO3-1.5((CeO2)@ZnO2) Ball milling is carried out according to the ratio of balls to water =1:2:1 to obtain slurry, and the slurry is dried to obtain a formula material;
step two: ball milling is carried out for 12 hours according to the formula materials, the binder and the water are =1:1.4:1.2 to obtain slurry, the slurry is sieved and stirred at a low speed and then is sent into a drying tower to obtain the product d50Processing materials which are 0.15mm spherical, and then pressing the processing materials into a green body of the microwave ceramic filter device by using a press;
step three: placing the microwave ceramic filter device blank in a kiln, firing at 1340 ℃, preserving heat for 4 hours, and naturally cooling to obtain a microwave ceramic filter device;
step four: and spraying or dipping a layer of electrode on the microwave ceramic filter ceramic part, firing at 900 ℃, keeping the temperature for 0.5 hour, naturally cooling, and manufacturing input and output end electrodes to obtain the microwave ceramic filter device.
The density of the microwave ceramic filter device blank in the second step is 2.5g/cm3(ii) a The binder is a mixed solution of polyvinyl alcohol and polyethylene glycol with the concentration of 10%, wherein the molar ratio of the polyvinyl alcohol to the polyethylene glycol is 10: 0.3.
The thickness of the electrode in the fourth step is 10 um.
The microwave dielectric ceramic material has a Q value of 6300(10GHz), a dielectric constant of 20.3, and a frequency temperature coefficient absolute value of 4 x 10-6/℃。
Example 5
（1）95Mg1.15TiO3-5CaTiO3-0.5((Pr6011)@ZnO2)-0.4((Nd2O3)@ZnO2) Preparation of microwave dielectric ceramic material
A microwave dielectric ceramic material is prepared from 95Mg (100 wt.%)1.15TiO3-5CaTiO3And 0.5 wt.% ((Pr)6011)@ZnO2) And 0.4 wt.% ((Nd)2O3)@ZnO2) Mixing to obtain the final product.
The low-temperature sintering aid ((Pr)6011)@ZnO2) The preparation steps are as follows:
the method comprises the following steps: will analytically pure Pr6011Ball milling for 6 hours to obtain d50Particles of 0.8 um;
step two: weighing Pr obtained in the first step according to the molar ratio of 1:2.176011Particles and Zn (NO)3)26H2O powder;
step three: according to step II Pr6011The amount of the raw materials is measured according to the molar ratio of 1:114, distilled water is poured into the container containing Pr6011Dispersing the particles in a container by using an ultrasonic cleaner for 30 minutes to obtain a solution A;
step four: according to step two Zn (NO)3)26H2Measuring the amount of O, measuring distilled water according to the molar ratio of 1:130, and pouring the distilled water into the container containing Zn (NO)3)26H2In a container of O powder, and then stirred with a glass rod for several minutes, Zn (NO)3)26H2Completely dissolving the O powder to obtain a B solution;
step five: adding magnetons into the solution A, then placing the solution A into a container with the water bath temperature of 70 ℃, placing the container on a magnetic stirrer platform for stirring, and then pouring the solution B into the solution A to obtain a mixed solution;
step six: dropwise adding ammonia water into the mixed solution, adjusting the pH value to 7, controlling the reaction time to be 50 minutes, standing for 28 hours after the reaction is finished, and then performing suction filtration, multiple washing and air drying to obtain a precipitate;
step seven: and putting the precipitate into a crucible for calcining, wherein the calcining temperature is 680 ℃, keeping the temperature for 30 minutes, and grinding the calcined product to obtain the low-temperature sintering aid.
The low-temperature sintering aid ((Nd)2O3)@ZnO2) The preparation steps are as follows:
the method comprises the following steps: will analytically pure Nd2O3Ball milling for 6 hours to obtain d50Particles of 0.8 um;
step two: nd obtained in the first step is weighed according to the molar ratio of 1:2.172O3Particles and Zn (NO)3)26H2O powder;
step three: according to step di Nd2O3The dosage of the Nd-containing material is measured according to the molar ratio of 1:124, and then the distilled water is poured into the Nd-containing material2O3Dispersing the particles in a container by using an ultrasonic cleaner for 30 minutes to obtain a solution A;
step four: according to step two Zn (NO)3)26H2Measuring the amount of O, measuring distilled water according to the molar ratio of 1:135, and pouring the distilled water into the container containing Zn (NO)3)26H2In a container of O powder, and then stirred with a glass rod for several minutes, Zn (NO)3)26H2Completely dissolving the O powder to obtain a B solution;
step five: adding magnetons into the solution A, then placing the solution A into a container with the water bath temperature of 70 ℃, placing the container on a magnetic stirrer platform for stirring, and then pouring the solution B into the solution A to obtain a mixed solution;
step six: dropwise adding ammonia water into the mixed solution, adjusting the pH value to 7, controlling the reaction time to be 60 minutes, standing for 24 hours after the reaction is finished, and then performing suction filtration, multiple washing and air drying to obtain a precipitate;
step seven: and putting the precipitate into a crucible for calcining, wherein the calcining temperature is 680 ℃, keeping the temperature for 30 minutes, and grinding the calcined product to obtain the low-temperature sintering aid.
The preparation steps of the basic powder material are as follows:
the method comprises the following steps: in proportion of 95Mg1.15TiO3-5CaTiO3Weighing MgO (d)501.2-1.8 um), CaCO3And TiO2Then preparing slurry according to the ratio of the material to the ball to the water =1:2: 2;
step two: the slurry prepared in the step one is screened, dried, dehydrated and calcined to synthesize microwave dielectric ceramic base powder;
d of MgO in the first step50Is 1.7 um; the firing system of the calcining procedure in the second step is as follows: increasing the temperature from room temperature to 400 ℃ in 180min, increasing the temperature from 400 ℃ to 900 ℃ in 180min, increasing the temperature from 900 ℃ to 1080 ℃ in 180min, and preserving the heat at 1080 ℃ for 240 min.
(2) Method for preparing microwave ceramic filter device by using microwave dielectric ceramic material
The method comprises the following steps: mixing 95Mg1.15TiO3-5CaTiO3-0.5((Pr6011)@ZnO2)-0.4((Nd2O3)@ZnO2) Ball milling is carried out according to the ratio of balls to water =1:2:1 to obtain slurry, and the slurry is dried to obtain a formula material;
step two: ball milling is carried out for 12 hours according to the formula materials, the binder and the water are =1:1.7:1.2 to obtain slurry, the slurry is sieved and stirred at a low speed and then is sent into a drying tower to obtain the product d50Processing materials which are 0.15mm spherical, and then pressing the processing materials into a green body of the microwave ceramic filter device by using a press;
step three: placing the microwave ceramic filter device blank in a kiln, firing at 1340 ℃, preserving heat for 4 hours, and naturally cooling to obtain a microwave ceramic filter device;
step four: and spraying or dipping a layer of electrode on the microwave ceramic filter ceramic part, firing at 900 ℃, keeping the temperature for 0.5 hour, naturally cooling, and manufacturing input and output end electrodes to obtain the microwave ceramic filter device.
The density of the microwave ceramic filter device blank in the second step is 2.5g/cm3(ii) a The binder is a mixed solution of polyvinyl alcohol and polyethylene glycol with the concentration of 10%, wherein the molar ratio of the polyvinyl alcohol to the polyethylene glycol is 10: 0.3.
The thickness of the electrode in the fourth step is 10 um.
The microwave dielectric ceramic material has a Q value of 7200(10GHz), a dielectric constant of 20.8 and an absolute value of a frequency temperature coefficient of 8 multiplied by 10-6/℃。
Claims (4)
1. A microwave dielectric ceramic material is characterized in that: the microwave dielectric ceramic material is prepared by mixing 100 wt% of microwave dielectric ceramic base powder and 0.6-2 wt% of low-temperature sintering aid, and the chemical composition formula of the microwave dielectric ceramic base powder is as follows: 95Mg1.15TiO3-5CaTiO3The low-temperature sintering aid is ZnO2A rare earth oxide-coated composition;
the low-temperature sintering aid is composed of one or more compositions;
the rare earth oxide is Pr6011、Nd2O3One of (1);
the preparation steps of the basic powder material are as follows:
the method comprises the following steps: in proportion of 95Mg1.15TiO3-5CaTiO3Weighing MgO and CaCO3And TiO2Then preparing slurry according to the ratio of the material to the ball to the water =1:2: 2;
step two: the slurry prepared in the step one is screened, dried, dehydrated and calcined to synthesize microwave dielectric ceramic base powder;
d of MgO in the first step501.2-1.8 um; the firing system of the calcining procedure in the second step is as follows: heating from room temperature to 400 deg.C for 180min, heating from 400 deg.C to 900 deg.C for 180min, heating from 900 deg.C to 1080 deg.C for 180min, and maintaining at 1080 deg.C for 240 min;
the preparation steps of the low-temperature sintering aid are as follows:
the method comprises the following steps: ball milling analytically pure rare earth oxide for 6 hours to obtain d50Particles of 0.8 um;
step two: weighing the rare earth oxide particles obtained in the step one and Zn (NO) according to the molar ratio of 1.16:13)2·6H2O powder;
step three: according to the dosage of the rare earth oxide in the step two, measuring distilled water according to the molar ratio of 1:114, pouring the distilled water into a container containing rare earth oxide particles, and dispersing for 30 minutes by using an ultrasonic cleaner to obtain a solution A;
step four: according to step two Zn (NO)3)2·6H2Measuring the amount of O, measuring distilled water according to the molar ratio of 1:130, and pouring the distilled water into the container containing Zn (NO)3)2·6H2In a container of O powder, and then stirred with a glass rod for several minutes, Zn (NO)3)2·6H2Completely dissolving the O powder to obtain a B solution;
step five: putting the magneton into the solution A, putting the solution A into a container with a water bath temperature of 62-82 ℃, putting the container on a magnetic stirrer platform for stirring, and pouring the solution B into the solution A to obtain a mixed solution;
step six: dropwise adding ammonia water into the mixed solution, adjusting the pH value to 7, controlling the reaction time to be 25-60 minutes, standing for 28 hours after the reaction is finished, and then performing suction filtration, multiple washing and air drying to obtain a precipitate;
step seven: and putting the precipitate into a crucible for calcining, wherein the calcining temperature is 680 ℃, keeping the temperature for 30 minutes, and grinding the calcined product to obtain the low-temperature sintering aid.
The Q value of the microwave dielectric ceramic material at 10GHz is 6800-7200, the dielectric constant is 20.2-20.8, and the absolute value of the temperature coefficient of frequency is 12 multiplied by 10-6Below/° c.
2. A method for preparing a microwave ceramic filter device by using the microwave dielectric ceramic material as claimed in claim 1, which is characterized by comprising the following steps:
the method comprises the following steps: ball-milling a microwave dielectric ceramic material according to the ratio of balls to water =1:2:1 to obtain slurry, and drying to obtain a formula material;
step two: ball milling is carried out for 12 hours according to the formula materials, the binder and the water are =1: 0.6-1.8: 1.2 to obtain slurry, the slurry is sieved and stirred at a low speed and then is sent into a drying tower to obtain the product d50Processing materials with the spherical shape of 0.15mm are pressed into a green body of the microwave ceramic filter by a press;
step three: placing the microwave ceramic filter device blank in a kiln, firing at 1340 ℃, preserving heat for 4 hours, and naturally cooling to obtain a microwave ceramic filter device;
step four: and spraying or dipping a layer of electrode on the microwave ceramic filter ceramic part, firing at 900 ℃, keeping the temperature for 0.5 hour, naturally cooling, and manufacturing input and output end electrodes to obtain the microwave ceramic filter device.
3. The method of claim 2, wherein: the density of the microwave ceramic filter device blank in the second step is 2.5g/cm3(ii) a The binder is a mixed solution of polyvinyl alcohol and polyethylene glycol with the concentration of 10%, wherein the molar ratio of the polyvinyl alcohol to the polyethylene glycol is 10: 0.3.
4. The method of claim 2, wherein: the thickness of the electrode in the fourth step is 10 um.
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