CN111995395B - Preparation of Zn-doped CaZrO3Method for microwave dielectric ceramic - Google Patents
Preparation of Zn-doped CaZrO3Method for microwave dielectric ceramic Download PDFInfo
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- CN111995395B CN111995395B CN202010936195.6A CN202010936195A CN111995395B CN 111995395 B CN111995395 B CN 111995395B CN 202010936195 A CN202010936195 A CN 202010936195A CN 111995395 B CN111995395 B CN 111995395B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000010438 heat treatment Methods 0.000 claims abstract description 49
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 22
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 239000011575 calcium Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910002976 CaZrO3 Inorganic materials 0.000 claims abstract description 13
- 235000019441 ethanol Nutrition 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003825 pressing Methods 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 238000012360 testing method Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 8
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims 1
- 239000005642 Oleic acid Substances 0.000 claims 1
- 235000021355 Stearic acid Nutrition 0.000 claims 1
- 239000001110 calcium chloride Substances 0.000 claims 1
- 229910001628 calcium chloride Inorganic materials 0.000 claims 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 229910052573 porcelain Inorganic materials 0.000 claims 1
- 239000008117 stearic acid Substances 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000004891 communication Methods 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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Abstract
The invention discloses a method for preparing Zn-doped CaZrO3The method of microwave dielectric ceramic includes the following steps: (1) dissolving tetrabutyl zirconate in absolute ethyl alcohol to form a tetrabutyl zirconate ethyl alcohol solution; (2) dissolving inorganic salt of zinc and inorganic salt of calcium in absolute ethyl alcohol according to a doping ratio to form a mixed solution of zinc salt and calcium salt; (3) slowly adding a mixed solution of zinc salt and calcium salt into a tetrabutyl zirconate ethanol solution according to the molar ratio of (zinc + calcium) to zirconium of 1:1, and adding a dispersing agent; (4) adding nitric acid to adjust the pH value; (5) standing the sol to fully gelatinize the sol; (6) drying the gel at 80 ℃, and performing heat treatment at 700-900 ℃ to obtain powder; (7) adding PVA into the powder for granulation, and pressing and forming by a tablet machine; (8) sintering at 1250-1350 ℃; (9) and (5) testing the dielectric property. The invention reduces the CaZrO3The sintering temperature of the microwave dielectric ceramic improves the dielectric property of the microwave dielectric ceramic; the sintering temperature was reduced from above 1550 ℃ to 1350 ℃.
Description
Technical Field
The invention relates to a preparation method of microwave dielectric ceramic, in particular to a preparation method of Zn-doped CaZrO3The microwave dielectric ceramic is suitable for preparing microwave components such as filters, antennas, capacitors and the like, and belongs to the field of material science.
Background
Microwave dielectric ceramics are a new functional ceramic which is rapidly developed in recent years, and are widely applied to mobile communication, satellite communication, military radar and the like as microwave components such as resonators, filters, dielectric antennas, dielectric guided wave loops and the like. In recent years, the development of microwave communication technology is rapid, and communication terminals are required to be miniaturized, integrated, multifunctional and low in cost as much as possible.
CaZrO3The microwave dielectric ceramic has a proper dielectric constant and low dielectric loss, so that the microwave dielectric ceramic has good practical value as a capacitor and a dielectric resonator under the microwave condition, but the sintering temperature is extremely high, and the manufacturing cost of the microwave dielectric ceramic in practical application is greatly increased. Sunshan Shuichi paper Bisborate ternary pair CaZr03Influence of Low-temperature sintering of microwave dielectric ceramics by CaZrO3In which BaO-Bi is added2O3-B2O3(BBB) ternary compound and Bi2O3-ZnO-B2O3(BZB) ternary compound for effectively reducing CaZrO3The sintering temperature of the ceramic is higher, but the amount of the additive is larger, so that CaZrO3The quality factor of the microwave dielectric ceramic is seriously reduced. Therefore, the development of an effective CaZrO reduction method is urgently needed3The sintering temperature of the microwave dielectric ceramic is kept, and the high quality factor is kept.
Disclosure of Invention
The invention aims to overcome CaZrO3The microwave medium has the defect of high sintering temperature and high quality factor, and adopts tetrabutyl zirconate, inorganic zinc salt, inorganic calcium salt, dispersant, nitric acid, absolute ethyl alcohol and polyvinyl alcohol as raw materials to prepare Zn-doped CaZrO by a sol-gel method3A method for preparing microwave dielectric ceramics.
The invention is realized by the following technical scheme.
Preparation of Zn-doped CaZrO3The method for preparing the microwave dielectric ceramic comprises the following steps:
(1) dissolving tetrabutyl zirconate in absolute ethyl alcohol to form a tetrabutyl zirconate ethyl alcohol solution;
(2) dissolving inorganic salt of zinc and inorganic salt of calcium in absolute ethyl alcohol according to a doping ratio, wherein the ratio of zinc: calcium ═ x: (1-x), wherein x is 0.01, 0.02, 0.03, 0.04, 0.05, to form a mixed solution of zinc salt and calcium salt;
(3) slowly adding the mixed solution of zinc salt and calcium salt into the tetrabutyl zirconate ethanol solution according to the molar ratio of (zinc + calcium) to zirconium of 1:1, and adding a proper amount of dispersant;
(4) adding a proper amount of nitric acid;
(5) standing the sol to fully gelatinize the sol;
(6) drying the gel at 80 ℃, and performing heat treatment at 700-900 ℃ to obtain powder;
(7) adding PVA into the powder for granulation, and then pressing and forming by using a powder tablet machine;
(8) putting the green body formed by pressing in the step (7) into a sintering furnace, sintering at 1250-1350 ℃, and preserving heat for 4 hours to obtain the microwave dielectric ceramic
(9) And (4) carrying out dielectric property test on the microwave dielectric ceramic prepared in the step (8).
And (4) continuously stirring in the steps (1) to (4) at a rotating speed of 300r/min by using an electric stirrer.
The precursor concentration of the step (3) is controlled to be 0.75mol/L-1.5 mol/L.
The addition amount standard of the nitric acid in the step (4) is H+：Zr4+Is 0.1.
The heating rate of the heat treatment in the step (6) is 5 ℃/min, and the heat preservation time is 1 h.
The PVA added in the step (7) is a PVA solution with the concentration of 5wt%, the adding amount is 8wt% of the powder, the forming pressure is 4MPa, the diameter of the green body is 16mm, and the height is 8 mm.
The sintering system in the step (8) is that the temperature is raised to 200 ℃ at the speed of 3 ℃/min and is kept for 1h, and the temperature is raised to 500 ℃ at the speed of 3 ℃/min and is kept for 2 h; heating to the target temperature at the speed of 2 ℃/min and preserving the heat for 4 h.
The method has the beneficial effects that by using a sol-gel method combined with a doping modification method, the CaZrO content is reduced3The sintering temperature of the microwave dielectric ceramic improves the dielectric property of the microwave dielectric ceramic; the sintering temperature is reduced from more than 1550 ℃ to 1350 DEG Cr＝28.31—29.58，Q·f＝21500—35400GHz，τf＝-24.3—-18.5 10-6/℃。
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the examples.
Example 1
Step 1: weighing 1mol of Zr (C)4H9O)4Dissolving in 1L of absolute ethyl alcohol to form a tetrabutyl zirconate absolute ethyl alcohol solution with the concentration of 1 mol/L; 0.01mol of Zn (NO) is weighed3)2·6H2O and 0.99mol of Ca (NO)3)2·4H2Dissolving O in 1L of absolute ethyl alcohol to form a zinc nitrate and calcium nitrate mixed solution with the total concentration of 1 mol/L.
Step 2: slowly adding the mixed solution of zinc nitrate and calcium nitrate into the tetrabutyl zirconate ethanol solution in the stirring process, and then adding polyethylene glycol accounting for 2 wt% of the mixed solution; 0.1mol of nitric acid was added to the mixed solution.
And 3, step 3: standing the sol for 24h to ensure that the sol is fully gelatinized, putting the sol into an oven at 80 ℃ for drying, then putting the sol into a sintering furnace, heating the sol to 800 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 1h to obtain Zn0.01Ca0.99ZrO3And (3) powder.
And 4, step 4: adding PVA solution with the concentration of 5wt% and the mass of the powder of 8wt%, grinding and granulating, and pressing into a green body with the diameter of 16mm and the height of 8mm by a tablet machine at the pressure of 4 MPa.
And 5: putting the pressed and molded blank into a sintering furnace, heating to 200 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 1h, and heating to 500 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 h; heating up to 1350 ℃ at the heating rate of 2 ℃/min and preserving heat for 4h to prepare the microwave dielectric ceramic; and finally, carrying out a dielectric property test.
Example 2
Step 1: weighing 1mol of Zr (C)4H9O)4Dissolving in 1L of absolute ethyl alcohol to form a tetrabutyl zirconate absolute ethyl alcohol solution with the concentration of 1 mol/L; 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.98mol of Ca (NO)3)2·4H2Dissolving O in 1L of absolute ethyl alcohol to form a zinc nitrate and calcium nitrate mixed solution with the total concentration of 1 mol/L.
Step 2: slowly adding the mixed solution of zinc nitrate and calcium nitrate into the tetrabutyl zirconate ethanol solution in the stirring process, and then adding polyethylene glycol accounting for 2 wt% of the mixed solution; 0.1mol of nitric acid was added to the mixed solution.
And 3, step 3: standing the sol for 24h to ensure that the sol is fully gelatinized, putting the sol into an oven at 80 ℃ for drying, then putting the sol into a sintering furnace, heating the sol to 800 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 1h to obtain Zn0.02Ca0.98ZrO3And (3) powder.
And 4, step 4: adding PVA solution with the concentration of 5wt% and the mass of the powder of 8wt%, grinding and granulating, and pressing into a green body with the diameter of 16mm and the height of 8mm by a tablet machine at the pressure of 4 MPa.
And 5: putting the pressed and molded blank into a sintering furnace, heating to 200 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 1h, and heating to 500 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 h; heating up to 1350 ℃ at the heating rate of 2 ℃/min and preserving heat for 4h to prepare the microwave dielectric ceramic; and finally, carrying out a dielectric property test.
Example 3
Step 1: weighing 1mol of Zr (C)4H9O)4Dissolving in 1L of absolute ethyl alcohol to form a tetrabutyl zirconate absolute ethyl alcohol solution with the concentration of 1 mol/L; 0.3 of Zn (NO) was weighed3)2·6H2O and 0.97mol of Ca (NO)3)2·4H2Dissolving O in 1L of absolute ethyl alcohol to form a zinc nitrate and calcium nitrate mixed solution with the total concentration of 1 mol/L.
Step 2: slowly adding the mixed solution of zinc nitrate and calcium nitrate into the tetrabutyl zirconate ethanol solution in the stirring process, and then adding polyethylene glycol accounting for 2 wt% of the mixed solution; 0.1mol of nitric acid was added to the mixed solution.
And 3, step 3: standing the sol for 24h to ensure that the sol is fully gelatinized, putting the sol into an oven at 80 ℃ for drying, then putting the sol into a sintering furnace, heating the sol to 800 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 1h to obtain Zn0.03Ca0.97ZrO3And (3) powder.
And 4, step 4: adding PVA solution with the concentration of 5wt% and the mass of the powder of 8wt%, grinding and granulating, and pressing into a green body with the diameter of 16mm and the height of 8mm by a tablet machine at the pressure of 4 MPa.
And 5: putting the pressed and molded blank into a sintering furnace, heating to 200 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 1h, and heating to 500 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 h; heating up to 1350 ℃ at the heating rate of 2 ℃/min and preserving heat for 4h to prepare the microwave dielectric ceramic; and finally, carrying out a dielectric property test.
Example 4
Step 1: weighing 1mol of Zr (C)4H9O)4Dissolving in 1L of absolute ethyl alcohol to form a tetrabutyl zirconate absolute ethyl alcohol solution with the concentration of 1 mol/L; 0.04mol of Zn (NO) is weighed3)2·6H2O and 0.96mol of Ca (NO)3)2·4H2Dissolving O in 1L absolute ethyl alcohol to form a total concentration of 1molA mixed solution of zinc nitrate and calcium nitrate.
Step 2: slowly adding the mixed solution of zinc nitrate and calcium nitrate into the tetrabutyl zirconate ethanol solution in the stirring process, and then adding polyethylene glycol accounting for 2 wt% of the mixed solution; 0.1mol of nitric acid was added to the mixed solution.
And step 3: standing the sol for 24h to ensure that the sol is fully gelatinized, putting the sol into an oven at 80 ℃ for drying, then putting the sol into a sintering furnace, heating the sol to 800 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 1h to obtain Zn0.04Ca0.96ZrO3And (3) powder.
And 4, step 4: adding PVA solution with the concentration of 5wt% and the mass of the powder of 8wt%, grinding and granulating, and pressing into a green body with the diameter of 16mm and the height of 8mm by a tablet machine at the pressure of 4 MPa.
And 5: putting the pressed and molded blank into a sintering furnace, heating to 200 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 1h, and heating to 500 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 h; heating up to 1350 ℃ at the heating rate of 2 ℃/min and preserving heat for 4h to prepare the microwave dielectric ceramic; and finally, carrying out a dielectric property test.
Example 5
Step 1: weighing 1mol of Zr (C)4H9O)4Dissolving in 1L of absolute ethyl alcohol to form a tetrabutyl zirconate absolute ethyl alcohol solution with the concentration of 1 mol/L; 0.05mol of Zn (NO) is weighed3)2·6H2O and 0.95mol of Ca (NO)3)2·4H2Dissolving O in 1L of absolute ethyl alcohol to form a zinc nitrate and calcium nitrate mixed solution with the total concentration of 1 mol/L.
Step 2: slowly adding the mixed solution of zinc nitrate and calcium nitrate into the tetrabutyl zirconate ethanol solution in the stirring process, and then adding polyethylene glycol accounting for 2 wt% of the mixed solution; 0.1mol of nitric acid was added to the mixed solution.
And step 3: standing the sol for 24h to ensure that the sol is fully gelatinized, putting the sol into an oven at 80 ℃ for drying, then putting the sol into a sintering furnace, heating the sol to 800 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 1h to obtain Zn0.05Ca0.95ZrO3And (3) powder.
And 4, step 4: adding PVA solution with the concentration of 5wt% and the mass of the powder of 8wt%, grinding and granulating, and pressing into a green body with the diameter of 16mm and the height of 8mm by a tablet machine at the pressure of 4 MPa.
And 5: putting the pressed and molded blank into a sintering furnace, heating to 200 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 1h, and heating to 500 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 h; heating up to 1350 ℃ at the heating rate of 2 ℃/min and preserving heat for 4h to prepare the microwave dielectric ceramic; and finally, carrying out a dielectric property test.
The detection results of various key parameters and dielectric properties of the embodiment of the invention are detailed in table 1.
TABLE 1
From the test results, it can be seen that the filter quality factor Q × f of all the examples>20000GHz higher than that of undoped CaZrO3The quality factor (Q × f is 9000-3The sintering temperature of the ceramic powder improves the quality factor of the ceramic powder. CaZrO3The dielectric constant of the system is reduced from 29.58 to 28.31 along with the increase of doping amount, the quality factor is increased and then reduced along with the increase of doping amount, and the quality factor is highest when the doping amount of the metallic zinc is 0.03 (Q multiplied by f is 29400GHz), CaZrO3The temperature coefficients of the frequencies of the system are all small, and are increased from-24.3 multiplied by 10 along with the increase of the doping amount-6The temperature was reduced to-18.5X 10-6/℃。
Claims (4)
1. Preparation of Zn-doped CaZrO3The method for preparing microwave dielectric ceramic comprises the following steps:
(1) dissolving tetrabutyl zirconate in absolute ethyl alcohol to form a tetrabutyl zirconate ethyl alcohol solution;
(2) dissolving inorganic salt of zinc and inorganic salt of calcium in absolute ethyl alcohol according to a doping ratio, wherein the ratio of zinc: calcium = x: (1-x), wherein x =0.01, 0.02, 0.03, 0.04, 0.05, and a mixed solution of zinc salt and calcium salt is formed;
the inorganic salt of zinc is Zn (NO)3)2·6H2O or ZnCl2(ii) a The inorganic salt of calcium is Ca (NO)3)2·4H2O or CaCl2(ii) a The dispersant is one or more of polyethylene glycol, oleic acid and stearic acid;
(3) slowly adding a mixed solution of zinc salt and calcium salt into a tetrabutyl zirconate ethanol solution according to the molar ratio of zinc, calcium and zirconium of 1:1, and adding a proper amount of a dispersing agent; the concentration of the zirconic acid tetrabutyl ester ethanol solution is controlled to be 0.75mol/L-1.5 mol/L;
(4) adding a proper amount of nitric acid; the addition amount standard of the nitric acid is H+：Zr4+In a molar ratio of 0.1: 1;
(5) standing the sol to fully gelatinize the sol;
(6) drying the gel at 80 ℃, and performing heat treatment at 700-900 ℃ to obtain powder;
(7) adding PVA into the powder for granulation, and then pressing and forming by using a powder tablet machine;
(8) putting the green body formed by pressing in the step (7) into a sintering furnace, sintering at 1250-1350 ℃, and preserving heat for 4 hours to obtain microwave dielectric ceramic; the sintering system is that the temperature is raised to 200 ℃ at the speed of 3 ℃/min and is preserved for 1h, and the temperature is raised to 500 ℃ at the speed of 3 ℃/min and is preserved for 2 h; heating to the target temperature at the speed of 2 ℃/min and preserving heat for 4 h;
(9) and (4) carrying out dielectric property test on the microwave dielectric ceramic prepared in the step (8).
2. Preparation of Zn-doped CaZrO according to claim 13The method for microwave dielectric ceramics is characterized in that the steps (1) to (4) are continuously stirred by using an electric stirrer at the rotating speed of 300 r/min.
3. Preparation of Zn-doped CaZrO according to claim 13The method for preparing the microwave dielectric ceramic is characterized in that the heating rate of the heat treatment in the step (6) is 5 ℃/min, and the heat preservation time is 1 h.
4. Preparation of Zn-doped CaZrO according to claim 13Microwave medium potteryThe method for preparing the porcelain is characterized in that the PVA added in the step (7) is a PVA solution with the concentration of 5wt%, the adding amount is 8wt% of the mass of the powder, the forming pressure is 4MPa, the diameter of the green body is 16mm, and the height is 8 mm.
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| SU810643A1 (en) * | 1979-02-12 | 1981-03-07 | Предприятие П/Я А-1695 | Charge composition for making ceramic material with high dielectric permeability |
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| CN104761258A (en) * | 2015-03-18 | 2015-07-08 | 河南科技大学 | Method of low-temperature sintering calcium zirconate microwave dielectric ceramic |
| CN109824085A (en) * | 2019-03-29 | 2019-05-31 | 四川大学 | A kind of pure perovskite phase calcium zirconate process for preparing nm-class powder |
| CN110937894A (en) * | 2019-12-24 | 2020-03-31 | 红河学院 | A, B-site co-doped calcium zirconate conductor material and preparation method thereof |
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| SU810643A1 (en) * | 1979-02-12 | 1981-03-07 | Предприятие П/Я А-1695 | Charge composition for making ceramic material with high dielectric permeability |
| CN102020465A (en) * | 2010-11-04 | 2011-04-20 | 仙桃市中星电子材料有限公司 | Multilayered ceramic capacitor medium ceramic material with reducing resistance |
| CN102354599A (en) * | 2011-06-30 | 2012-02-15 | 广东风华高新科技股份有限公司 | Preparation method for temperature compensation type multi-layer ceramic chip capacitor |
| CN104761258A (en) * | 2015-03-18 | 2015-07-08 | 河南科技大学 | Method of low-temperature sintering calcium zirconate microwave dielectric ceramic |
| CN109824085A (en) * | 2019-03-29 | 2019-05-31 | 四川大学 | A kind of pure perovskite phase calcium zirconate process for preparing nm-class powder |
| CN110937894A (en) * | 2019-12-24 | 2020-03-31 | 红河学院 | A, B-site co-doped calcium zirconate conductor material and preparation method thereof |
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