WO2023093221A1 - Preparation method for high-stability low-loss microwave dielectric ceramic material, and microwave dielectric ceramic material prepared by applying same - Google Patents
Preparation method for high-stability low-loss microwave dielectric ceramic material, and microwave dielectric ceramic material prepared by applying same Download PDFInfo
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- WO2023093221A1 WO2023093221A1 PCT/CN2022/118279 CN2022118279W WO2023093221A1 WO 2023093221 A1 WO2023093221 A1 WO 2023093221A1 CN 2022118279 W CN2022118279 W CN 2022118279W WO 2023093221 A1 WO2023093221 A1 WO 2023093221A1
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000919 ceramic Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000011812 mixed powder Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 36
- 239000011575 calcium Substances 0.000 claims description 34
- 229910052791 calcium Inorganic materials 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 13
- 229910052712 strontium Inorganic materials 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims 2
- 238000005507 spraying Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000012545 processing Methods 0.000 description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 238000011056 performance test Methods 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229910001954 samarium oxide Inorganic materials 0.000 description 5
- 229940075630 samarium oxide Drugs 0.000 description 5
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 150000001206 Neodymium Chemical class 0.000 description 1
- 150000001216 Samarium Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
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Definitions
- the invention belongs to the field of ceramic materials, and in particular relates to a preparation method of a high-stability and low-loss microwave dielectric ceramic material and a microwave dielectric ceramic material prepared by using the same.
- Microwave dielectric ceramic materials are a new class of electronic ceramic materials that have developed rapidly in recent years. It is the basic material of various dielectric resonators, filters, vibrators, duplexers, antennas and other devices, and has a large number of applications in microwave communications, satellite navigation, and military radar equipment. With the construction of national 5G communication base stations, its usage is more extensive.
- Microwave dielectric ceramics with a dielectric constant ⁇ r of about 20 are currently a type of ceramic material widely used in satellite communications and 5G base stations. In order to overcome many problems caused by the application of different microwave frequency bands, such materials are required to meet high quality factor QF, near zero temperature frequency coefficient ⁇ f, and the price should be cheap.
- the preparation of microwave dielectric ceramics includes powder preparation and molding stages.
- stage of powder preparation the traditional method of oxide powder mixed ball milling, pre-calcination, crushing, and dry pressing is usually used.
- the particle size of the powder is not well controlled, the particle size distribution is wide, the required sintering temperature is high, and the grains are prone to abnormal growth, which affects the dielectric properties and consistency.
- the particle size is not uniform It will also lead to uneven shrinkage of the product after sintering, which will affect the dimensional accuracy and increase the difficulty of subsequent debugging.
- the object of the present invention is to provide a method for preparing a high-stability and low-loss microwave dielectric ceramic material and the microwave dielectric ceramic material prepared by using the same, so as to optimize the microwave performance of the microwave dielectric ceramic material.
- a method for preparing a microwave dielectric ceramic material with high stability and low loss comprising the following steps: Step 1, weighing raw materials according to the chemical composition of the microwave dielectric ceramic material, the raw materials include magnesium source material, calcium source material, titanium source material, strontium source material, samarium source material, neodymium source material, and aluminum source material; step 2, mixing and crushing the raw materials to obtain a mixed powder; step 3, making the mixed powder at 1000-1350°C Calcining at low temperature for 1.5 to 4 hours to obtain a calcined product; Step 4, crushing the calcined product, and adding an adhesive to it to prepare a ceramic green body; Step 5, calcining the green body in a high-temperature furnace until the calcining temperature reaches 1300- 1500°C, keep warm for 3-10 minutes, then lower the calcination temperature by 150-250°C within 5 minutes, continue to keep warm for 8-13 hours; step 6, cool naturally to get the finished product.
- the magnesium source material is selected from at least one of magnesium oxide, magnesium salt, and magnesium hydroxide
- the calcium source material is selected from at least one of calcium oxide, calcium salt, and calcium hydroxide
- the titanium source material is selected from From at least one of titanium dioxide and titanate
- the strontium source material is selected from at least one of strontium oxide and strontium salt
- the samarium source material is selected from at least one of samarium oxide and samarium salt
- the neodymium source material is selected from From at least one of neodymium oxide and neodymium salt
- the aluminum source material is selected from at least one of alumina, aluminum salt, and aluminum hydroxide.
- step 4 also includes the operation of spray granulation: performing spray granulation on the crushed calcined product and the binder to obtain pellets, and dry pressing the pellets to obtain a ceramic green body.
- the crushing process in step 4 is as follows: ball milling the calcined material for 18-22 hours, and then sand-milling the obtained powder for 15-40 minutes.
- the heating rate is 5-12° C./min.
- a microwave dielectric ceramic material prepared by the above preparation method is provided.
- the microwave dielectric ceramic material is a (Mg, Ca)TiO 3 series ceramic material; in the raw materials for preparing the microwave dielectric ceramic material, the molar ratio of Mg element, Ca element and Ti element is 0.8 ⁇ 1.2:0.1 ⁇ 0.9:1 ⁇ 1.5.
- the microwave dielectric ceramic material is a MRAIO 4 -series ceramic material, wherein the element type of M includes at least one of Sr element and Ca element, and the element type of R includes La element, Nd element, Sm element, and Y element. At least one; in the raw materials for preparing the microwave dielectric ceramic material, the molar ratio of the element represented by M, the element represented by R and the element Al is 6-8:5-6:5-7.
- the element types of M are Sr element and Ca element, and the element type of R is Sm element.
- the molar ratio of the Sr element to the Ca element is 0.09-0.15:1.
- the MRAIO 4 series ceramic material is a titanium-doped ceramic material; in the raw materials for preparing the microwave dielectric ceramic material, the molar ratio of Ti element to Al element is 0.12-0.2:1.
- the present invention can reduce the calcination time of the green body at high temperature, make the green body denser at a lower calcination temperature, and avoid the abnormal growth of crystal grains during the calcination process, which will cause Particle size distribution range is too wide. Furthermore, the sand milling process is adopted in the powder making process, so that the fineness of the powder particles is higher and the particle size division is more concentrated. Moreover, the above preparation method is simple to operate, and the required calcination process can be provided by using conventional equipment, which is suitable for large-scale production. By applying the above method, a microwave dielectric ceramic material with a dielectric constant ⁇ r of about 20 can be prepared. The ceramic material has uniform crystal grains, high quality factor QF and near-zero temperature frequency coefficient ⁇ f .
- Fig. 1 is (Mg, Ca) TiO prepared by processing IA group in embodiment 1 The SEM figure of the microwave dielectric ceramic material;
- Fig. 2 is (Mg, Ca) TiO prepared by processing IB group in embodiment 1 The SEM figure of the microwave dielectric ceramic material;
- FIG. 3 is a SEM image of (Mg, Ca)TiO 3 microwave dielectric ceramic material prepared by treating the IC group in Example 1.
- FIG. 3 is a SEM image of (Mg, Ca)TiO 3 microwave dielectric ceramic material prepared by treating the IC group in Example 1.
- the raw materials used in the preparation of the microwave dielectric ceramic material in this embodiment are electronic grade magnesium oxide, calcium carbonate and titanium dioxide.
- Step 1 using an analytical balance to accurately weigh 397.41g of magnesium oxide, 78.47g of calcium carbonate, and 967.74g of titanium dioxide;
- Step 2 the mixture obtained by mixing the above raw materials is ball milled and mixed for 20 hours, dried and crushed;
- Step 3 calcining the mixed powder at 1150°C for 2 hours to obtain a calcined product
- Step 4 the calcined material is ball milled and mixed for 20 hours, and then the material is introduced into a sand mill for 30 minutes, and a binder is added to the fine particles thus obtained, and the obtained material is subjected to spray granulation to obtain aggregates,
- the pellets are dry-pressed with a pressure of 60Mpa to make A cylinder with a height of 7.5 mm is obtained as a ceramic green body;
- Step 5 First remove the glue in the tunnel kiln, then raise the temperature to 1350°C at a rate of 10°C/min, keep it warm for 5 minutes, then lower the calcination temperature to 1150°C within 5 minutes, and keep it at this temperature for 10 minutes Hour;
- Step 6 natural cooling to prepare microwave dielectric ceramic material (Mg, Ca)TiO 3 .
- Process IB group to prepare (Mg, Ca)TiO 3 The steps of microwave dielectric ceramic material are as follows:
- Step 2 keep consistent with the treatment of IA group
- Step 3 keep consistent with the processing of IA group
- Step 4 keep consistent with the processing of IA group
- Step 5 deglue the green body in the tunnel kiln first, then raise the temperature to 1150°C at a speed of 10°C/min, and keep it warm for 10 hours;
- Step 6 natural cooling to prepare microwave dielectric ceramic material (Mg, Ca)TiO 3 .
- Step 2 keep consistent with the treatment of IA group
- Step 3 keep consistent with the processing of IA group
- Step 4 keep consistent with the processing of IA group
- Step 5 debinding the green body in the tunnel kiln first, then raising the temperature to 1350°C at a rate of 10°C/min, keeping it warm for 5 minutes, and then reducing the calcining temperature to 1150°C at a rate of 20°C/h;
- Step 6 natural cooling to prepare microwave dielectric ceramic material (Mg, Ca)TiO 3 .
- Microwave dielectric ceramic materials prepared according to the methods provided by treatment group IA, treatment IB, and treatment IC group participated in the microwave performance test. Each treatment group took 5 repetitions, and each piece of microwave dielectric ceramic material was 1 repetition. Microwave performance was performed at 4-9 GHz using an Agilent network analyzer. The results of the microwave performance test are shown in Tables 1-3 respectively.
- the dielectric constant and temperature frequency coefficient of (Mg, Ca)TiO 3 microwave ceramics produced by the IA group are very stable, and they are distributed in a concentrated range of values.
- the QF value can reach more than 65,000, which belongs to relatively high level.
- the green body was calcined at a lower temperature in the treatment group IB, and there was no obvious temperature change during the calcination process, and the QF value of the prepared ceramic material did not exceed 50,000.
- the particle size of the ceramic materials prepared by treating Group IA and Group IB is relatively uniform, without serious sintering or agglomeration.
- the ceramic materials produced by the treatment group IC have obvious agglomeration, and the particle size is different. Over time, it is prone to abnormal growth and reunion.
- the temperature-frequency coefficient difference at different temperatures of the ceramic materials prepared in the IC group is more than 15, which is significantly higher than the corresponding values of the ceramic powders in the IA group and the IB group.
- the dielectric constant is also high , the numerical distribution is relatively unstable. It can be seen that (Mg, Ca)TiO 3 microwave dielectric ceramics with a dielectric constant of about 20 can be obtained by processing group IA. 3 The quality factor QF and the temperature frequency coefficient ⁇ f of ceramic materials have been greatly improved.
- Table 1 deals with the microwave properties of microwave dielectric ceramic materials prepared by IA group
- Table 2 handles the microwave performance of the microwave dielectric ceramic material prepared by IB group
- the raw materials used in the preparation of the microwave dielectric ceramic material in this embodiment are electronic grade calcium carbonate, samarium oxide, aluminum oxide and titanium dioxide.
- Step 1 using an analytical balance to accurately weigh 740.32g of calcium carbonate, 905.03g of samarium oxide, 328.55g of aluminum oxide, and 74.11g of titanium dioxide;
- Step 2 the mixture obtained by mixing the above raw materials is ball milled and mixed for 20 hours, dried and crushed;
- Step 3 calcining the mixed powder at 1250°C for 2 hours to obtain a calcined product
- Step 4 the calcined material is ball milled and mixed for 20 hours, and then the material is introduced into a sand mill for 25 minutes, and a binder is added to the fine particles thus obtained, and the obtained material is subjected to spray granulation to obtain aggregates,
- the pellets are dry-pressed with a pressure of 60Mpa to make A cylinder with a height of 7.5mm is obtained as a ceramic green body;
- Step 5 Degumming the green body in the tunnel kiln first, then raising the temperature to 1450°C at a speed of 10°C/min, keeping it warm for 5 minutes, then reducing the calcination temperature to 1250°C within 5 minutes, and keeping it at this temperature for 10 minutes Hour;
- Step 6 natural cooling to prepare the microwave dielectric ceramic material CaSmAlO 4 .
- Step 1 is consistent with the treatment of Group II A;
- Step 5 deglue the green body in the tunnel kiln first, then raise the temperature to 1250°C at a speed of 10°C/min, and keep it warm for 10 hours;
- Step 6 natural cooling to prepare the microwave dielectric ceramic material CaSmAlO 4 .
- Step 1 is consistent with the treatment of Group II A;
- Step 5 debinding the green body in the tunnel kiln first, then raising the temperature to 1450°C at a rate of 10°C/min, keeping it warm for 5 minutes, and then reducing the calcining temperature to 1250°C at a rate of 20°C/h;
- Step 6 natural cooling to prepare the microwave dielectric ceramic material CaSmAlO 4 .
- the dielectric constant and the temperature frequency coefficient of the CaSmAlO 4 microwave dielectric ceramics produced by the treatment group II A are very stable, and they are distributed in a concentrated range of values. In addition, the QF value can reach more than 85,000, which belongs to a relatively high level. .
- Table 4 handles the microwave performance of the microwave dielectric ceramic material prepared by II A group
- Table 5 handles the microwave performance of the microwave dielectric ceramic material prepared by II B group
- Table 6 handles the microwave performance of the microwave dielectric ceramic material prepared by II C group
- the raw materials used in the preparation of the microwave dielectric ceramic material in this embodiment are electronic grade strontium carbonate, calcium carbonate, samarium oxide, aluminum oxide and titanium dioxide.
- Step 1 using an analytical balance to accurately weigh 108.20 g of strontium carbonate, 648.93 g of calcium carbonate, 950.98 g of samarium oxide, 261.55 g of aluminum oxide and 72.18 g of titanium dioxide;
- Step 2 the mixture obtained by mixing the above raw materials is ball milled and mixed for 20 hours, dried and crushed;
- Step 3 calcining the mixed powder at 1000°C for 2 hours to obtain a calcined product
- Step 4 the calcined material is ball milled and mixed for 20 hours, and then the material is introduced into a sand mill for 35 minutes, and a binder is added to the fine particles thus obtained, and the obtained material is subjected to spray granulation to obtain aggregates,
- the pellets are dry-pressed with a pressure of 60Mpa to make A cylinder with a height of 7.5mm is obtained as a ceramic green body;
- Step 5 the green body is degummed first in the tunnel kiln, and then the temperature is raised to 1485°C at a speed of 10°C/min, and kept for 5 minutes, and then the calcination temperature is reduced to 1300°C within 5 minutes, and kept at this temperature for 10 minutes. Hour;
- Step 6 natural cooling to prepare microwave dielectric ceramic material (Sr, Ca)SmAlO 4 .
- Process IIIB group to prepare (Sr, Ca) SmAlO 4 The steps of microwave dielectric ceramic material are as follows:
- Step 5 deglue the green body in the tunnel kiln first, then raise the temperature to 1300°C at a speed of 10°C/min, and keep it warm for 10 hours;
- Step 6 natural cooling to prepare microwave dielectric ceramic material (Sr, Ca)SmAlO 4 .
- Step 5 debinding the green body in the tunnel kiln first, then raising the temperature to 1485°C at a rate of 10°C/min, keeping it warm for 5 minutes, and then reducing the calcination temperature to 1300°C at a rate of 18.5°C/h;
- Step 6 natural cooling to prepare microwave dielectric ceramic material (Sr, Ca)SmAlO 4 .
- Microwave dielectric ceramic materials prepared according to the methods provided by treatment group IIIA, treatment group IIIB, and treatment group IIIC participated in the microwave performance test. Each treatment group took 5 repetitions, and each piece of microwave dielectric ceramic material was 1 repetition. Microwave performance was performed at 4-9 GHz using an Agilent network analyzer. The results of the microwave performance test are shown in Tables 7-9 respectively.
- the dielectric constant and temperature frequency coefficient of (Sr, Ca)SmAlO 4 microwave dielectric ceramics produced by Group IIIA are very stable, and they are distributed in a concentrated range of values. In addition, the QF value can reach more than 95,000, which belongs to higher level.
- the green body was calcined at a lower temperature in the treatment of group IIIB, and there was no obvious temperature change during the calcination process, and the QF value of the prepared ceramic material could only reach 70,000-90,000.
- the temperature drops slowly, and the particles are kept at high temperature for a long time.
- the corresponding numerical values of the ceramic powders of Group IIIA and Group IIIB are relatively high, and the distribution of numerical values is relatively unstable. It can be seen that (Sr, Ca)SmAlO 4 microwave dielectric ceramics with a dielectric constant of about 20 can be obtained by treating group IIIA. 4
- the quality factor QF and the temperature frequency coefficient ⁇ f of ceramic materials have been greatly improved.
- Table 7 treats the microwave performance of the microwave dielectric ceramic material prepared by Group IIIA
- Table 8 handles the microwave performance of the microwave dielectric ceramic material prepared by IIIB group
- Table 9 handles the microwave performance of the microwave dielectric ceramic material prepared by IIIC group
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Abstract
A preparation method for a high-stability low-loss microwave dielectric ceramic material, comprising the following steps: weighing raw materials according to the chemical composition of the microwave dielectric ceramic material; mixing and crushing the raw materials to obtain mixed powder; calcining the mixed powder at 1000-1350°C for 1.5-4 hours to obtain a pre-sintered object; crushing the pre-sintered object, and adding an adhesive thereto to prepare a ceramic green body; calcining the green body in a high-temperature furnace until the calcining temperature reaches 1300-1500°C, keeping the temperature for 3-10 minutes, then reducing the calcining temperature by 150-250°C within 5 minutes, and continuously keeping the temperature for 8-13 hours; and naturally cooling to obtain a finished product. By applying the method, a microwave dielectric ceramic material having a dielectric constant εr of about 20 can be prepared; the ceramic material is uniform in crystal grains, and has a high quality factor QF and a near-zero temperature frequency coefficient τf.
Description
本发明属于陶瓷材料领域，具体地，涉及一种高稳定低损耗的微波介质陶瓷材料的制备方法及应用其制得的微波介质陶瓷材料。The invention belongs to the field of ceramic materials, and in particular relates to a preparation method of a high-stability and low-loss microwave dielectric ceramic material and a microwave dielectric ceramic material prepared by using the same.
微波介质陶瓷材料是近年来迅速发展的一类新型电子陶瓷材料。它是各种介质谐振器、滤波器、振动器、双工器、天线等器件的基础材料，在微波通信、卫星导航、军用雷达设备中有大量应用。随着国家5G通信基站的建设，其用量更加广泛。Microwave dielectric ceramic materials are a new class of electronic ceramic materials that have developed rapidly in recent years. It is the basic material of various dielectric resonators, filters, vibrators, duplexers, antennas and other devices, and has a large number of applications in microwave communications, satellite navigation, and military radar equipment. With the construction of national 5G communication base stations, its usage is more extensive.
介电常数εr为20左右的微波介质陶瓷是目前在卫星通信和5G基站中用量很大的一类陶瓷材料。为克服不同微波频段应用带来的众多问题，需要这类材料满足高品质因数QF，近零的温度频率系数τf，并且价格要便宜。Microwave dielectric ceramics with a dielectric constant εr of about 20 are currently a type of ceramic material widely used in satellite communications and 5G base stations. In order to overcome many problems caused by the application of different microwave frequency bands, such materials are required to meet high quality factor QF, near zero temperature frequency coefficient τf, and the price should be cheap.
微波介质陶瓷的制备包括粉体制备和成型阶段。在粉体制备的阶段，通常采用氧化物粉末混合球磨、预烧、破碎、干压成型这一传统方法。在该传统方法的处理过程中，粉体的粒度控制不到位，粒度分布宽，需要的烧结温度较高，晶粒容易出现异常长大，从而影响介电性能和一致性，此外，粒度不均匀也会导致产品在烧结后的收缩不均匀，影响尺寸精度，增加了后续调试的难度。除了上述传统方法之外，为了保证粉体的粒度均匀度，也可以通过各种水热法制备纳米粉体，用于后续的成型阶段。但是，纳米粉体的生产过程繁琐，生产成本高。微波介质陶瓷材料的成型通常在隧道窑中进行烧结，这种加热烧结方式的烧结时间较长，很容易导致晶粒的异常长大。SPS、微波烧结炉等加热设备可以替代传统的隧道窑进行粉体的烧结成型，但是这些新设备价格昂贵，单次处理量偏低，不利于常规生产。The preparation of microwave dielectric ceramics includes powder preparation and molding stages. In the stage of powder preparation, the traditional method of oxide powder mixed ball milling, pre-calcination, crushing, and dry pressing is usually used. In the processing process of this traditional method, the particle size of the powder is not well controlled, the particle size distribution is wide, the required sintering temperature is high, and the grains are prone to abnormal growth, which affects the dielectric properties and consistency. In addition, the particle size is not uniform It will also lead to uneven shrinkage of the product after sintering, which will affect the dimensional accuracy and increase the difficulty of subsequent debugging. In addition to the above-mentioned traditional methods, in order to ensure the uniformity of the particle size of the powder, various hydrothermal methods can also be used to prepare nano-powders for subsequent molding stages. However, the production process of nano powder is cumbersome and the production cost is high. The molding of microwave dielectric ceramic materials is usually sintered in a tunnel kiln. The sintering time of this heating and sintering method is long, which can easily lead to abnormal growth of grains. SPS, microwave sintering furnace and other heating equipment can replace the traditional tunnel kiln for powder sintering and molding, but these new equipment are expensive and the single processing capacity is low, which is not conducive to conventional production.
发明内容Contents of the invention
本发明的目的在于提供一种高稳定低损耗的微波介质陶瓷材料的制备方法及应用其制得的微波介质陶瓷材料，以优化微波介质陶瓷材料的微波性能。The object of the present invention is to provide a method for preparing a high-stability and low-loss microwave dielectric ceramic material and the microwave dielectric ceramic material prepared by using the same, so as to optimize the microwave performance of the microwave dielectric ceramic material.
根据本发明的一个方面，提供一种高稳定低损耗的微波介质陶瓷材料的制备方法，包括以下步骤：步骤一，按照微波介质陶瓷材料的化学组成称取原料，原料包括镁源物质、钙源物质、钛源物质、锶源物质、钐源物质、钕源物质、铝源物质中的至少两种；步骤二，混合并破碎原料，得到混合粉末；步骤三，使混合粉末在1000～1350℃下煅烧1.5～4小时，得到预烧物；步骤四，破碎预烧物，并向其中添加粘接剂，制备陶瓷生坯；步骤五，在高温炉中煅烧生坯，至煅烧温度达到1300～1500℃，保温3～10分钟，然后，使煅烧温度在5分钟内降低150～250℃，继续保温8～13小时；步骤六，自然冷却，制得成品。According to one aspect of the present invention, a method for preparing a microwave dielectric ceramic material with high stability and low loss is provided, comprising the following steps: Step 1, weighing raw materials according to the chemical composition of the microwave dielectric ceramic material, the raw materials include magnesium source material, calcium source material, titanium source material, strontium source material, samarium source material, neodymium source material, and aluminum source material; step 2, mixing and crushing the raw materials to obtain a mixed powder; step 3, making the mixed powder at 1000-1350°C Calcining at low temperature for 1.5 to 4 hours to obtain a calcined product; Step 4, crushing the calcined product, and adding an adhesive to it to prepare a ceramic green body; Step 5, calcining the green body in a high-temperature furnace until the calcining temperature reaches 1300- 1500°C, keep warm for 3-10 minutes, then lower the calcination temperature by 150-250°C within 5 minutes, continue to keep warm for 8-13 hours; step 6, cool naturally to get the finished product.
可选地，所述镁源物质选自氧化镁、镁盐、氢氧化镁中的至少一种，钙源物质选自氧化钙、钙盐、氢氧化钙中的至少一种，钛源物质选自二氧化钛、钛酸盐中的至少一种，锶源物质选自氧化锶、锶盐中的至少一种，所述钐源物质选自氧化钐、钐盐中的至少一种，钕源物质选自氧化钕、钕盐中的至少一种，铝源物质选自氧化铝、铝盐、氢氧化铝中的至少一种。Optionally, the magnesium source material is selected from at least one of magnesium oxide, magnesium salt, and magnesium hydroxide, the calcium source material is selected from at least one of calcium oxide, calcium salt, and calcium hydroxide, and the titanium source material is selected from From at least one of titanium dioxide and titanate, the strontium source material is selected from at least one of strontium oxide and strontium salt, the samarium source material is selected from at least one of samarium oxide and samarium salt, and the neodymium source material is selected from From at least one of neodymium oxide and neodymium salt, the aluminum source material is selected from at least one of alumina, aluminum salt, and aluminum hydroxide.
优选地，在步骤四中还包括喷雾造粒的操作：使经过破碎后的预烧物与粘接剂进行喷雾造粒得到团粒，干压团粒，制得陶瓷生坯。Preferably, step 4 also includes the operation of spray granulation: performing spray granulation on the crushed calcined product and the binder to obtain pellets, and dry pressing the pellets to obtain a ceramic green body.
优选地，在步骤四中的破碎工艺为：对预烧物进行球磨处理18～22小时，然后对由此得到的粉末进行砂磨处理15～40分钟。Preferably, the crushing process in step 4 is as follows: ball milling the calcined material for 18-22 hours, and then sand-milling the obtained powder for 15-40 minutes.
优选地，在步骤五中，在升温过程中，升温速率为5～12℃/min。Preferably, in step five, during the heating process, the heating rate is 5-12° C./min.
根据本发明的另一个方面，提供一种应用上述制备方法制得的微波介质陶瓷材料。According to another aspect of the present invention, a microwave dielectric ceramic material prepared by the above preparation method is provided.
优选地，微波介质陶瓷材料为(Mg，Ca)TiO
3系陶瓷材料；在制备微波介质陶瓷材料的原料中，Mg元素、Ca元素和Ti元素摩尔比为0.8～1.2∶0.1～0.9∶1～1.5。
Preferably, the microwave dielectric ceramic material is a (Mg, Ca)TiO 3 series ceramic material; in the raw materials for preparing the microwave dielectric ceramic material, the molar ratio of Mg element, Ca element and Ti element is 0.8～1.2:0.1～0.9:1～ 1.5.
优选地，微波介质陶瓷材料为MRAlO
4系陶瓷材料，其中，M的元素种类包括Sr元素、Ca元素中的至少一种，R的元素种类包括La元素、Nd元素、Sm元素、Y元素中的至少一种；在制备微波介质陶瓷材料的原料中，以M为代表的元素、以R为代表的元素和Al元素摩尔比为6～8∶5～6∶5～7。
Preferably, the microwave dielectric ceramic material is a MRAIO 4 -series ceramic material, wherein the element type of M includes at least one of Sr element and Ca element, and the element type of R includes La element, Nd element, Sm element, and Y element. At least one; in the raw materials for preparing the microwave dielectric ceramic material, the molar ratio of the element represented by M, the element represented by R and the element Al is 6-8:5-6:5-7.
优选地，M的元素种类为Sr元素和Ca元素，R的元素种类为Sm元素。Preferably, the element types of M are Sr element and Ca element, and the element type of R is Sm element.
优选地，在制备微波介质陶瓷材料的原料中，Sr元素和Ca元素的摩尔比为0.09～0.15∶1。Preferably, in the raw materials for preparing the microwave dielectric ceramic material, the molar ratio of the Sr element to the Ca element is 0.09-0.15:1.
优选地，MRAlO
4系陶瓷材料为钛掺杂的陶瓷材料；在制备微波介质陶瓷材料的原料中，Ti元素和Al元素的摩尔比为0.12～0.2∶1。
Preferably, the MRAIO 4 series ceramic material is a titanium-doped ceramic material; in the raw materials for preparing the microwave dielectric ceramic material, the molar ratio of Ti element to Al element is 0.12-0.2:1.
本发明通过设计微波介质陶瓷材料的煅烧工艺，能够缩减坯体在高温下的煅烧时间，使坯体在较低的煅烧温度下实现密致化，避免晶粒在煅烧过程中异常长大而导致粒度分布范围过宽。进一步地，在制粉的过程中采用砂磨工艺，使粉体颗粒细度更高、粒度分度更集中。而且，上述制备方法操作简单，使用常规的设备即可提供所需的煅烧工艺，适合大生产。应用上述方法可以制得介电常数εr为20左右的微波介质陶瓷材料，该陶瓷材料晶粒均匀，同时兼具高品质因数QF和近零的温度频率系数τ
f。
By designing the calcination process of the microwave dielectric ceramic material, the present invention can reduce the calcination time of the green body at high temperature, make the green body denser at a lower calcination temperature, and avoid the abnormal growth of crystal grains during the calcination process, which will cause Particle size distribution range is too wide. Furthermore, the sand milling process is adopted in the powder making process, so that the fineness of the powder particles is higher and the particle size division is more concentrated. Moreover, the above preparation method is simple to operate, and the required calcination process can be provided by using conventional equipment, which is suitable for large-scale production. By applying the above method, a microwave dielectric ceramic material with a dielectric constant εr of about 20 can be prepared. The ceramic material has uniform crystal grains, high quality factor QF and near-zero temperature frequency coefficient τ f .
图1为实施例1中处理IA组制备的(Mg，Ca)TiO
3微波介质陶瓷材料的SEM图；
Fig. 1 is (Mg, Ca) TiO prepared by processing IA group in embodiment 1 The SEM figure of the microwave dielectric ceramic material;
图2为实施例1中处理IB组制备的(Mg，Ca)TiO
3微波介质陶瓷材料的SEM图；
Fig. 2 is (Mg, Ca) TiO prepared by processing IB group in embodiment 1 The SEM figure of the microwave dielectric ceramic material;
图3为实施例1中处理IC组制备的(Mg，Ca)TiO
3微波介质陶瓷材料的SEM图。
FIG. 3 is a SEM image of (Mg, Ca)TiO 3 microwave dielectric ceramic material prepared by treating the IC group in Example 1. FIG.
为了使本技术领域的人员更好地理解本发明方案，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。In order to enable those skilled in the art to better understand the present invention, the following will clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the present invention, rather than Full examples.
实施例1Example 1
1.(Mg，Ca)TiO
3微波介质陶瓷的制备
1. Preparation of (Mg, Ca)TiO 3 microwave dielectric ceramics
本实施例用于制备微波介质陶瓷材料的原料为电子级的氧化镁、碳酸钙和二氧化钛。The raw materials used in the preparation of the microwave dielectric ceramic material in this embodiment are electronic grade magnesium oxide, calcium carbonate and titanium dioxide.
(1)处理IA组(1) Dealing with Group IA
处理IA组制备(Mg，Ca)TiO
3微波介质陶瓷材料的步骤如下：
The steps for preparing (Mg, Ca)TiO microwave dielectric ceramic materials in Group IA are as follows:
步骤一，利用分析天平准确称量氧化镁397.41g、碳酸钙78.47g、二氧化钛967.74g；Step 1, using an analytical balance to accurately weigh 397.41g of magnesium oxide, 78.47g of calcium carbonate, and 967.74g of titanium dioxide;
步骤二，使上述原料混合得到的混合物经过球磨混合20小时，烘干后破碎；Step 2, the mixture obtained by mixing the above raw materials is ball milled and mixed for 20 hours, dried and crushed;
步骤三，使混合粉末在1150℃煅烧2小时，得到预烧物；Step 3, calcining the mixed powder at 1150°C for 2 hours to obtain a calcined product;
步骤四，使预烧物经过球磨混合20小时，然后再将物料引入到砂磨机中处理30分钟，向由此得到的细颗粒中加入粘结剂，使所得物料经过喷雾造粒得到团粒，在成型模具中以60Mpa的压力将团粒干压成型，制成
高7.5mm的圆柱得到陶瓷生坯；
Step 4, the calcined material is ball milled and mixed for 20 hours, and then the material is introduced into a sand mill for 30 minutes, and a binder is added to the fine particles thus obtained, and the obtained material is subjected to spray granulation to obtain aggregates, In the forming mold, the pellets are dry-pressed with a pressure of 60Mpa to make A cylinder with a height of 7.5 mm is obtained as a ceramic green body;
步骤五，将生坯在隧道窑中先排胶，然后以10℃/min的速度升温到1350℃，保温5分钟，然后在5分钟内使煅烧温度降至1150℃，在此温度下保温10小时；Step 5: First remove the glue in the tunnel kiln, then raise the temperature to 1350°C at a rate of 10°C/min, keep it warm for 5 minutes, then lower the calcination temperature to 1150°C within 5 minutes, and keep it at this temperature for 10 minutes Hour;
步骤六，自然冷却，制得微波介质陶瓷材料(Mg，Ca)TiO
3。
Step 6, natural cooling to prepare microwave dielectric ceramic material (Mg, Ca)TiO 3 .
(2)处理IB组(2) Dealing with Group IB
处理IB组制备(Mg，Ca)TiO
3微波介质陶瓷材料的步骤如下：
Process IB group to prepare (Mg, Ca)TiO 3 The steps of microwave dielectric ceramic material are as follows:
步骤一，与处理IA组保持一致；Step 1, consistent with the treatment of IA group;
步骤二，与处理IA组保持一致；Step 2, keep consistent with the treatment of IA group;
步骤三，与处理IA组保持一致；Step 3, keep consistent with the processing of IA group;
步骤四，与处理IA组保持一致；Step 4, keep consistent with the processing of IA group;
步骤五，将生坯在隧道窑中先排胶，然后以10℃/min的速度升温到1150℃，保温10小时；Step 5, deglue the green body in the tunnel kiln first, then raise the temperature to 1150°C at a speed of 10°C/min, and keep it warm for 10 hours;
步骤六，自然冷却，制得微波介质陶瓷材料(Mg，Ca)TiO
3。
Step 6, natural cooling to prepare microwave dielectric ceramic material (Mg, Ca)TiO 3 .
(3)处理IC组(3) Process IC group
处理IC组制备(Mg，Ca)TiO
3微波介质陶瓷材料的步骤如下：
The steps for preparing (Mg, Ca)TiO microwave dielectric ceramic materials by processing the IC group are as follows:
步骤一，与处理IA组保持一致；Step 1, consistent with the treatment of IA group;
步骤二，与处理IA组保持一致；Step 2, keep consistent with the treatment of IA group;
步骤三，与处理IA组保持一致；Step 3, keep consistent with the processing of IA group;
步骤四，与处理IA组保持一致；Step 4, keep consistent with the processing of IA group;
步骤五，将生坯在隧道窑中先排胶，然后以10℃/min的速度升温到1350℃，保温5分钟，然后以20℃/h的速率使煅烧温度降至1150℃；Step 5, debinding the green body in the tunnel kiln first, then raising the temperature to 1350°C at a rate of 10°C/min, keeping it warm for 5 minutes, and then reducing the calcining temperature to 1150°C at a rate of 20°C/h;
步骤六，自然冷却，制得微波介质陶瓷材料(Mg，Ca)TiO
3。
Step 6, natural cooling to prepare microwave dielectric ceramic material (Mg, Ca)TiO 3 .
2.微波性能测试2. Microwave performance test
在本实施例提供的三组处理组制备The three groups of treatment groups provided in this example were prepared
以分别按照处理IA组、处理IB组、处理IC组提供的方法制备的微波介质陶瓷材料参与微波性能测试，每个处理组取5个重复，每片微波介质陶瓷材料为1个重复。采用安捷伦网络分析仪，在4-9GHz频率下进行微波性能。微波性能测试的结果分别如表1～3所示。处理IA组制作的(Mg，Ca)TiO
3微波陶瓷的介电常数和不同温度下的温度频率系数都十分稳定，分别分布在集中的数值范围内，另外，QF值可以达到65000以上，属于较高的水平。然而，处理IB组采用较低的温度煅烧坯体，煅烧的过程中没有明显幅度的变温，其制备的陶瓷材料的QF值最高不超过50000。如图1、图2所示，处理IA组和处理IB组所制得的陶瓷材料的颗粒粒度都较为均匀，无严重的烧结或团聚。相对而言，如图3所示，处理IC组所制得的陶瓷材料 出现明显的团聚，颗粒大小不一，处理IC组的坯体煅烧过程中，温度下降的速度慢，颗粒处于高温下的时间长，容易出现异常长大和团聚。而处理IC组制得的陶瓷材料的不同温度下的温度频率系数差值达到15以上，显著高于处理IA组和处理IB组的陶瓷粉体的相应数值，另外，其介电常数也偏高，数值分布较为不稳定。由此可见，采用处理IA组可以获得介电常数约为20的(Mg，Ca)TiO
3微波介质陶瓷，相较于其他方法制得的产品，处理IA组制得的(Mg，Ca)TiO
3陶瓷材料的品质因素QF以及温度频率系数τf都得到较大改善。
Microwave dielectric ceramic materials prepared according to the methods provided by treatment group IA, treatment IB, and treatment IC group participated in the microwave performance test. Each treatment group took 5 repetitions, and each piece of microwave dielectric ceramic material was 1 repetition. Microwave performance was performed at 4-9 GHz using an Agilent network analyzer. The results of the microwave performance test are shown in Tables 1-3 respectively. The dielectric constant and temperature frequency coefficient of (Mg, Ca)TiO 3 microwave ceramics produced by the IA group are very stable, and they are distributed in a concentrated range of values. In addition, the QF value can reach more than 65,000, which belongs to relatively high level. However, the green body was calcined at a lower temperature in the treatment group IB, and there was no obvious temperature change during the calcination process, and the QF value of the prepared ceramic material did not exceed 50,000. As shown in Figure 1 and Figure 2, the particle size of the ceramic materials prepared by treating Group IA and Group IB is relatively uniform, without serious sintering or agglomeration. Relatively speaking, as shown in Figure 3, the ceramic materials produced by the treatment group IC have obvious agglomeration, and the particle size is different. Over time, it is prone to abnormal growth and reunion. However, the temperature-frequency coefficient difference at different temperatures of the ceramic materials prepared in the IC group is more than 15, which is significantly higher than the corresponding values of the ceramic powders in the IA group and the IB group. In addition, the dielectric constant is also high , the numerical distribution is relatively unstable. It can be seen that (Mg, Ca)TiO 3 microwave dielectric ceramics with a dielectric constant of about 20 can be obtained by processing group IA. 3 The quality factor QF and the temperature frequency coefficient τf of ceramic materials have been greatly improved.
表1处理IA组制备的微波介质陶瓷材料的微波性能Table 1 deals with the microwave properties of microwave dielectric ceramic materials prepared by IA group
表2处理IB组制备的微波介质陶瓷材料的微波性能Table 2 handles the microwave performance of the microwave dielectric ceramic material prepared by IB group
表3处理IC组制备的微波介质陶瓷材料的微波性能Table 3 Microwave properties of microwave dielectric ceramic materials prepared by processing IC group
实施例2Example 2
1.CaSmAlO
4微波介质陶瓷的制备
1. Preparation of CaSmAlO 4 microwave dielectric ceramics
本实施例用于制备微波介质陶瓷材料的原料为电子级的碳酸钙、氧化钐、三氧化二铝和二氧化钛。The raw materials used in the preparation of the microwave dielectric ceramic material in this embodiment are electronic grade calcium carbonate, samarium oxide, aluminum oxide and titanium dioxide.
(1)处理II A组(1) Treatment of Group II A
处理II A组制备CaSmAlO
4微波介质陶瓷材料的步骤如下：
The steps for preparing CaSmAlO microwave dielectric ceramic materials in group II A are as follows:
步骤一，利用分析天平准确称量碳酸钙740.32g、氧化钐905.03g、三氧化二铝328.55g、二氧化钛74.11g；Step 1, using an analytical balance to accurately weigh 740.32g of calcium carbonate, 905.03g of samarium oxide, 328.55g of aluminum oxide, and 74.11g of titanium dioxide;
步骤二，使上述原料混合得到的混合物经过球磨混合20小时，烘干后破碎；Step 2, the mixture obtained by mixing the above raw materials is ball milled and mixed for 20 hours, dried and crushed;
步骤三，使混合粉末在1250℃煅烧2小时，得到预烧物；Step 3, calcining the mixed powder at 1250°C for 2 hours to obtain a calcined product;
步骤四，使预烧物经过球磨混合20小时，然后再将物料引入到砂磨机中处理25分钟，向由此得到的细颗粒中加入粘结剂，使所得物料经过喷雾造粒得到团粒，在成型模具中以60Mpa的压力将团粒干压成型，制成
高7.5mm的圆柱得到陶瓷生坯；
Step 4, the calcined material is ball milled and mixed for 20 hours, and then the material is introduced into a sand mill for 25 minutes, and a binder is added to the fine particles thus obtained, and the obtained material is subjected to spray granulation to obtain aggregates, In the forming mold, the pellets are dry-pressed with a pressure of 60Mpa to make A cylinder with a height of 7.5mm is obtained as a ceramic green body;
步骤五，将生坯在隧道窑中先排胶，然后以10℃/min的速度升温到1450℃，保温5分钟，然后在5分钟内使煅烧温度降至1250℃，在此温度下保温10小时；Step 5: Degumming the green body in the tunnel kiln first, then raising the temperature to 1450°C at a speed of 10°C/min, keeping it warm for 5 minutes, then reducing the calcination temperature to 1250°C within 5 minutes, and keeping it at this temperature for 10 minutes Hour;
步骤六，自然冷却，制得微波介质陶瓷材料CaSmAlO
4。
Step 6, natural cooling to prepare the microwave dielectric ceramic material CaSmAlO 4 .
(2)处理II B组(2) Treatment of Group II B
处理II B组制备CaSmAlO
4微波介质陶瓷材料的步骤如下：
The steps of processing II B group to prepare CaSmAlO microwave dielectric ceramic material are as follows:
步骤一，与处理II A组保持一致；Step 1 is consistent with the treatment of Group II A;
步骤二，与处理II A组保持一致；Step 2, consistent with the treatment of Group II A;
步骤三，与处理II A组保持一致；Step 3, consistent with the treatment of Group II A;
步骤四，与处理II A组保持一致；Step 4, consistent with the treatment of Group II A;
步骤五，将生坯在隧道窑中先排胶，然后以10℃/min的速度升温到1250℃，保温10小时；Step 5, deglue the green body in the tunnel kiln first, then raise the temperature to 1250°C at a speed of 10°C/min, and keep it warm for 10 hours;
步骤六，自然冷却，制得微波介质陶瓷材料CaSmAlO
4。
Step 6, natural cooling to prepare the microwave dielectric ceramic material CaSmAlO 4 .
(3)处理II C组(3) Treatment of Group II C
处理II C组制备CaSmAlO
4微波介质陶瓷材料的步骤如下：
The steps for preparing CaSmAlO microwave dielectric ceramic materials in group II C are as follows:
步骤一，与处理II A组保持一致；Step 1 is consistent with the treatment of Group II A;
步骤二，与处理II A组保持一致；Step 2, consistent with the treatment of Group II A;
步骤三，与处理II A组保持一致；Step 3, consistent with the treatment of Group II A;
步骤四，与处理II A组保持一致；Step 4, consistent with the treatment of Group II A;
步骤五，将生坯在隧道窑中先排胶，然后以10℃/min的速度升温到1450℃，保温5分钟，然后以20℃/h的速率使煅烧温度降至1250℃；Step 5, debinding the green body in the tunnel kiln first, then raising the temperature to 1450°C at a rate of 10°C/min, keeping it warm for 5 minutes, and then reducing the calcining temperature to 1250°C at a rate of 20°C/h;
步骤六，自然冷却，制得微波介质陶瓷材料CaSmAlO
4。
Step 6, natural cooling to prepare the microwave dielectric ceramic material CaSmAlO 4 .
2.微波性能测试2. Microwave performance test
在本实施例提供的三组处理组制备The three groups of treatment groups provided in this example were prepared
以分别按照处理II A组、处理II B组、处理II C组提供的方法制备的微波介质陶瓷材料参与微波性能测试，每个处理组取5个重复，每片微波介质陶瓷材料为1个重复。采用安捷伦网络分析仪，在4-9GHz频率下进行微波性能。微波性能测试的结果分别如表4～6所示。处理II A组制作的CaSmAlO
4微波介质陶瓷的介电常数和不同温度下的温度频率系数都十分稳定，分别分布在集中的数值范围内，另外，QF值可以达到85000以上，属于较高的水平。然而，处理II B组采用较低的温度煅烧坯体，煅烧的过程中没有明显幅度的变温，其制备的陶瓷材料的QF值只能到50000～70000。处理II C组的坯体煅烧过程中，温度下降的速度慢，颗粒处于高温下的时间长，由此制得的陶瓷材料的不同温度下的温度频率系数差值达到5以上，，显著高于处理II A组和处理II B组的陶瓷粉体的相应数值，另外，其介电常数也偏高，数值分布较为不稳定。由此可见，采用处理II A组可以获得介电常数约为20的CaSmAlO
4微波介质陶瓷，相较于其他方法制得的产品，处理II A组制得的CaSmAlO
4陶瓷材料的品质因素QF以及温度频率系数τf都得到较大改善。
Microwave dielectric ceramic materials prepared according to the methods provided by treatment group II A, treatment II B, and treatment II C respectively participated in the microwave performance test. Each treatment group took 5 repetitions, and each piece of microwave dielectric ceramic material was 1 repetition. . Microwave performance was performed at 4-9 GHz using an Agilent network analyzer. The results of the microwave performance test are shown in Tables 4-6 respectively. The dielectric constant and the temperature frequency coefficient of the CaSmAlO 4 microwave dielectric ceramics produced by the treatment group II A are very stable, and they are distributed in a concentrated range of values. In addition, the QF value can reach more than 85,000, which belongs to a relatively high level. . However, lower temperature is used to calcine the green body in group II B, and there is no obvious temperature change during the calcination process, and the QF value of the prepared ceramic material can only reach 50,000-70,000. During the calcination process of the green body of the treatment group II C, the temperature drops slowly, and the particles stay at high temperature for a long time. The corresponding values of the ceramic powders treated with group II A and group II B, in addition, their dielectric constants are also high, and the distribution of values is relatively unstable. It can be seen that the CaSmAlO 4 microwave dielectric ceramics with a dielectric constant of about 20 can be obtained by processing II A group. Compared with products made by other methods, the quality factor QF and The temperature frequency coefficient τf has been greatly improved.
表4处理II A组制备的微波介质陶瓷材料的微波性能Table 4 handles the microwave performance of the microwave dielectric ceramic material prepared by II A group
表5处理II B组制备的微波介质陶瓷材料的微波性能Table 5 handles the microwave performance of the microwave dielectric ceramic material prepared by II B group
表6处理II C组制备的微波介质陶瓷材料的微波性能Table 6 handles the microwave performance of the microwave dielectric ceramic material prepared by II C group
实施例3Example 3
1.(Sr，Ca)SmAlO
4微波介质陶瓷的制备
1. Preparation of (Sr, Ca)SmAlO 4 microwave dielectric ceramics
本实施例用于制备微波介质陶瓷材料的原料为电子级的碳酸锶、碳酸钙、氧化钐、三氧化二铝和二氧化钛。The raw materials used in the preparation of the microwave dielectric ceramic material in this embodiment are electronic grade strontium carbonate, calcium carbonate, samarium oxide, aluminum oxide and titanium dioxide.
(1)处理IIIA组(1) Treatment of Group IIIA
处理IIIA组制备(Sr，Ca)SmAlO
4微波介质陶瓷材料的步骤如下：
The steps for preparing (Sr, Ca)SmAlO microwave dielectric ceramic materials from Group IIIA are as follows:
步骤一，利用分析天平准确称量碳酸锶108.20g、碳酸钙648.93g、氧化钐950.98g、三氧化二铝261.55g和二氧化钛72.18g；Step 1, using an analytical balance to accurately weigh 108.20 g of strontium carbonate, 648.93 g of calcium carbonate, 950.98 g of samarium oxide, 261.55 g of aluminum oxide and 72.18 g of titanium dioxide;
步骤二，使上述原料混合得到的混合物经过球磨混合20小时，烘干后破碎；Step 2, the mixture obtained by mixing the above raw materials is ball milled and mixed for 20 hours, dried and crushed;
步骤三，使混合粉末在1000℃煅烧2小时，得到预烧物；Step 3, calcining the mixed powder at 1000°C for 2 hours to obtain a calcined product;
步骤四，使预烧物经过球磨混合20小时，然后再将物料引入到砂磨机中处理35分钟，向由此得到的细颗粒中加入粘结剂，使所得物料经过喷雾造粒得到团粒，在成型模具中以60Mpa的压力将团粒干压成型，制成
高7.5mm的圆柱得到陶瓷生坯；
Step 4, the calcined material is ball milled and mixed for 20 hours, and then the material is introduced into a sand mill for 35 minutes, and a binder is added to the fine particles thus obtained, and the obtained material is subjected to spray granulation to obtain aggregates, In the forming mold, the pellets are dry-pressed with a pressure of 60Mpa to make A cylinder with a height of 7.5mm is obtained as a ceramic green body;
步骤五，将生坯在隧道窑中先排胶，然后以10℃/min的速度升温到1485℃，保温5分钟，然后在5分钟内使煅烧温度降至1300℃，在此温度下保温10小时；Step 5, the green body is degummed first in the tunnel kiln, and then the temperature is raised to 1485°C at a speed of 10°C/min, and kept for 5 minutes, and then the calcination temperature is reduced to 1300°C within 5 minutes, and kept at this temperature for 10 minutes. Hour;
步骤六，自然冷却，制得微波介质陶瓷材料(Sr，Ca)SmAlO
4。
Step 6, natural cooling to prepare microwave dielectric ceramic material (Sr, Ca)SmAlO 4 .
(2)处理IIIB组(2) Treatment of Group IIIB
处理IIIB组制备(Sr，Ca)SmAlO
4微波介质陶瓷材料的步骤如下：
Process IIIB group to prepare (Sr, Ca) SmAlO 4 The steps of microwave dielectric ceramic material are as follows:
步骤一，与处理IIIA组保持一致；Step 1, consistent with the treatment of group IIIA;
步骤二，与处理IIIA组保持一致；Step 2, consistent with the treatment of group IIIA;
步骤三，与处理IIIA组保持一致；Step 3, consistent with the treatment of group IIIA;
步骤四，与处理IIIA组保持一致；Step 4, consistent with the treatment of group IIIA;
步骤五，将生坯在隧道窑中先排胶，然后以10℃/min的速度升温到1300℃，保温10小时；Step 5, deglue the green body in the tunnel kiln first, then raise the temperature to 1300°C at a speed of 10°C/min, and keep it warm for 10 hours;
步骤六，自然冷却，制得微波介质陶瓷材料(Sr，Ca)SmAlO
4。
Step 6, natural cooling to prepare microwave dielectric ceramic material (Sr, Ca)SmAlO 4 .
(3)处理IIIC组(3) Treatment of Group IIIC
处理IIIC组制备(Sr，Ca)SmAlO
4微波介质陶瓷材料的步骤如下：
The steps for preparing (Sr, Ca)SmAlO microwave dielectric ceramic materials in Group IIIC are as follows:
步骤一，与处理IIIA组保持一致；Step 1, consistent with the treatment of group IIIA;
步骤二，与处理IIIA组保持一致；Step 2, consistent with the treatment of group IIIA;
步骤三，与处理IIIA组保持一致；Step 3, consistent with the treatment of group IIIA;
步骤四，与处理IIIA组保持一致；Step 4, consistent with the treatment of group IIIA;
步骤五，将生坯在隧道窑中先排胶，然后以10℃/min的速度升温到1485℃，保温5分钟，然后以18.5℃/h的速率使煅烧温度降至1300℃；Step 5, debinding the green body in the tunnel kiln first, then raising the temperature to 1485°C at a rate of 10°C/min, keeping it warm for 5 minutes, and then reducing the calcination temperature to 1300°C at a rate of 18.5°C/h;
步骤六，自然冷却，制得微波介质陶瓷材料(Sr，Ca)SmAlO
4。
Step 6, natural cooling to prepare microwave dielectric ceramic material (Sr, Ca)SmAlO 4 .
2.微波性能测试2. Microwave performance test
在本实施例提供的三组处理组制备The three groups of treatment groups provided in this example were prepared
以分别按照处理IIIA组、处理IIIB组、处理IIIC组提供的方法制备的微波介质陶瓷材料参与微波性能测试，每个处理组取5个重复，每片微波介质陶瓷材料为1个重复。采用安捷伦网络分析仪，在4-9GHz频率下进行微波性能。微波性能测试的结果分别如表7～9所示。处理IIIA组制作的(Sr，Ca)SmAlO
4微波介质陶瓷的介电常数和不同温度下的温度频率系数都十分稳定，分别分布在集中的数值范围内，另外，QF值可以达到95000以上，属于较高的水平。然而，处理IIIB组采用较低的温度煅烧坯体，煅烧的过程中没有明显幅度的变温，其制备的陶瓷材料的QF值只能到70000～90000。处理IIIC组的坯体煅烧过程中，温度下降的速度慢，颗粒处于高温下的时间长，由此制得的陶瓷材料的不同温度下的温度频率系数差值达到5以上，，显著高于处理IIIA组和处理IIIB组的陶瓷粉体的相应数值，另外，其介电常数也偏高，数值分布较为不稳定。由此可见，采用处理IIIA组可以获得介电常数约为20的(Sr，Ca)SmAlO
4微波介质陶瓷，相较于其他方法制得的产品，处理IIIA组制得的(Sr，Ca)SmAlO
4陶瓷材料的品质因素QF以及温度频率系数τf都得到较大改善。
Microwave dielectric ceramic materials prepared according to the methods provided by treatment group IIIA, treatment group IIIB, and treatment group IIIC participated in the microwave performance test. Each treatment group took 5 repetitions, and each piece of microwave dielectric ceramic material was 1 repetition. Microwave performance was performed at 4-9 GHz using an Agilent network analyzer. The results of the microwave performance test are shown in Tables 7-9 respectively. The dielectric constant and temperature frequency coefficient of (Sr, Ca)SmAlO 4 microwave dielectric ceramics produced by Group IIIA are very stable, and they are distributed in a concentrated range of values. In addition, the QF value can reach more than 95,000, which belongs to higher level. However, the green body was calcined at a lower temperature in the treatment of group IIIB, and there was no obvious temperature change during the calcination process, and the QF value of the prepared ceramic material could only reach 70,000-90,000. During the calcination process of the green body of the treatment group IIIC, the temperature drops slowly, and the particles are kept at high temperature for a long time. The corresponding numerical values of the ceramic powders of Group IIIA and Group IIIB are relatively high, and the distribution of numerical values is relatively unstable. It can be seen that (Sr, Ca)SmAlO 4 microwave dielectric ceramics with a dielectric constant of about 20 can be obtained by treating group IIIA. 4 The quality factor QF and the temperature frequency coefficient τf of ceramic materials have been greatly improved.
表7处理IIIA组制备的微波介质陶瓷材料的微波性能Table 7 treats the microwave performance of the microwave dielectric ceramic material prepared by Group IIIA
表8处理IIIB组制备的微波介质陶瓷材料的微波性能Table 8 handles the microwave performance of the microwave dielectric ceramic material prepared by IIIB group
表9处理IIIC组制备的微波介质陶瓷材料的微波性能Table 9 handles the microwave performance of the microwave dielectric ceramic material prepared by IIIC group
以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。The above embodiments are only used to illustrate the technical solution of the present invention rather than limiting the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solution of the present invention can be carried out Modification or equivalent replacement without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
- 一种高稳定低损耗的微波介质陶瓷材料的制备方法，其特征在于，包括以下步骤：A method for preparing a microwave dielectric ceramic material with high stability and low loss is characterized in that it comprises the following steps:步骤一，按照所述微波介质陶瓷材料的化学组成称取原料，所述原料包括镁源物质、钙源物质、钛源物质、锶源物质、钐源物质、钕源物质、铝源物质中的至少两种；Step 1, weighing raw materials according to the chemical composition of the microwave dielectric ceramic material, the raw materials include magnesium source materials, calcium source materials, titanium source materials, strontium source materials, samarium source materials, neodymium source materials, and aluminum source materials. at least two;步骤二，混合并破碎所述原料，得到混合粉末；Step 2, mixing and crushing the raw materials to obtain mixed powder;步骤三，使所述混合粉末在1000～1350℃下煅烧1.5～4小时，得到预烧物；Step 3, calcining the mixed powder at 1000-1350° C. for 1.5-4 hours to obtain a calcined product;步骤四，破碎所述预烧物，并向其中添加粘接剂，制备陶瓷生坯；Step 4, crushing the calcined material, and adding a binder to it to prepare a ceramic green body;步骤五，在高温炉中煅烧所述生坯，至煅烧温度达到1300～1500℃，保温3～10分钟，然后，使煅烧温度在5分钟内降低150～250℃，继续保温8～13小时；Step 5, calcining the green body in a high-temperature furnace until the calcining temperature reaches 1300-1500°C, and keeping it warm for 3-10 minutes, then lowering the calcining temperature by 150-250°C within 5 minutes, and continuing to keep it warm for 8-13 hours;步骤六，自然冷却，制得成品。Step 6, natural cooling to obtain the finished product.
- 如权利要求1所述高稳定低损耗的微波介质陶瓷材料的制备方法，其特征在于，在所述步骤四中还包括喷雾造粒的操作：使经过破碎后的所述预烧物与粘接剂进行喷雾造粒得到团粒，干压所述团粒，制得所述陶瓷生坯。The preparation method of the microwave dielectric ceramic material with high stability and low loss as claimed in claim 1 is characterized in that, in said step 4, the operation of spraying and granulating is also included: making said calcined material after crushing and bonding spray granulation to obtain granules, and dry press the granules to obtain the ceramic green body.
- 如权利要求2所述高稳定低损耗的微波介质陶瓷材料的制备方法，其特征在于，在所述步骤四中的破碎工艺为：对所述预烧物进行球磨处理18～22小时，然后对由此得到的粉末进行砂磨处理15～40分钟。The preparation method of the microwave dielectric ceramic material with high stability and low loss as claimed in claim 2, characterized in that, the crushing process in the step 4 is as follows: ball milling the calcined material for 18-22 hours, and then The powder thus obtained was sand-milled for 15-40 minutes.
- 如权利要求1所述高稳定低损耗的微波介质陶瓷材料的制备方法，其特征在于：在所述步骤五中，在升温过程中，升温速率为5～12℃/min。The method for preparing a high-stability and low-loss microwave dielectric ceramic material according to claim 1, characterized in that: in said step five, during the heating process, the heating rate is 5-12° C./min.
- 一种应用如权利要求1～4任一项所述制备方法制得的微波介质陶瓷材料。A microwave dielectric ceramic material prepared by applying the preparation method described in any one of claims 1-4.
- 如权利要求5所述微波介质陶瓷材料，其特征在于：Microwave dielectric ceramic material as claimed in claim 5, characterized in that:所述微波介质陶瓷材料为(Mg，Ca)TiO 3系陶瓷材料； The microwave dielectric ceramic material is (Mg, Ca)TiO 3 series ceramic material;在制备所述微波介质陶瓷材料的原料中，Mg元素、Ca元素和Ti元素摩尔比为0.8～1.2∶0.1～0.9∶1～1.5。In the raw materials for preparing the microwave dielectric ceramic material, the molar ratio of Mg element, Ca element and Ti element is 0.8-1.2:0.1-0.9:1-1.5.
- 如权利要求5所述微波介质陶瓷材料，其特征在于：Microwave dielectric ceramic material as claimed in claim 5, characterized in that:所述微波介质陶瓷材料为MRAlO 4系陶瓷材料，其中，所述M的元素种类包括Sr元素、Ca元素中的至少一种，所述R的元素种类包括La元素、Nd元素、Sm元素、Y元素中的至少一种； The microwave dielectric ceramic material is MRAIO 4 series ceramic material, wherein the element type of M includes at least one of Sr element and Ca element, and the element type of R includes La element, Nd element, Sm element, Y at least one of the elements;在制备所述微波介质陶瓷材料的原料中，以所述M为代表的元素、以所述R为代表的元素和Al元素摩尔比为6～8∶5～6∶5～7。In the raw materials for preparing the microwave dielectric ceramic material, the molar ratio of the element represented by M, the element represented by R and the element Al is 6-8:5-6:5-7.
- 如权利要求7所述微波介质陶瓷材料，其特征在于：所述M的元素种类为Sr元素和Ca元素，所述R的元素种类为Sm元素。The microwave dielectric ceramic material according to claim 7, wherein the element types of the M are Sr element and Ca element, and the element type of the R is Sm element.
- 如权利要求8所述微波介质陶瓷材料，其特征在于：在制备所述微波介质陶瓷材料的原料中，Sr元素和Ca元素的摩尔比为0.09～0.15∶1。The microwave dielectric ceramic material according to claim 8, characterized in that: in the raw materials for preparing the microwave dielectric ceramic material, the molar ratio of Sr element to Ca element is 0.09-0.15:1.
- 如权利要求7所述微波介质陶瓷材料，其特征在于：Microwave dielectric ceramic material as claimed in claim 7, characterized in that:所述MRAlO 4系陶瓷材料为钛掺杂的陶瓷材料； The MRAlO 4 series ceramic material is a titanium-doped ceramic material;在制备所述微波介质陶瓷材料的原料中，Ti元素和Al元素的摩尔比为0.12～0.2∶1。In the raw materials for preparing the microwave dielectric ceramic material, the molar ratio of Ti element to Al element is 0.12-0.2:1.
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