CN114276131B - Microwave dielectric ceramic material with medium dielectric constant and preparation method thereof - Google Patents
Microwave dielectric ceramic material with medium dielectric constant and preparation method thereof Download PDFInfo
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Abstract
The invention provides a microwave dielectric ceramic material with medium dielectric constant: the chemical composition of the compound is xCa (1－m) M m X n Ti (1－n) O 3 ‑yLaAlO 3 (ii) a M comprises at least one of magnesium element, barium element and strontium element; x comprises Zn element and at least one of vanadium subgroup element; x + y =1. The invention uses CaTiO 3 ‑LaAlO 3 Based on Sr, mg, ba to CaTiO 3 Ca in the calcium carbonate is substituted, and Zn and vanadium secondary group elements are used for replacing CaTiO 3 Substituted with Ti in (1), and the resulting substituent is reacted with LaAlO 3 The synthetic microwave dielectric ceramic material has good microwave performance, the dielectric constant of the ceramic material can be continuously adjusted and stably distributed, the dielectric constant of the ceramic material can reach about 45, the ceramic material also has a high-level QF value, and the temperature frequency coefficient is stable at different temperatures.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a microwave dielectric ceramic material with a medium dielectric constant and a preparation method thereof.
Background
Microwave dielectric ceramic materials are a new type of electronic ceramic materials which have been rapidly developed in recent years. It is the basic material of various dielectric resonators, filters, vibrators, duplexers, antennas and other devices, and has a great deal of application in microwave communication, satellite navigation and military radar equipment. With the development of national 5G communication, modern military communication and radar technology, the usage of the radar is wider.
The microwave dielectric ceramic with medium dielectric constant (dielectric constant Epsilon is about 45) is a ceramic material which is used in satellite communication and 5G base station at present and is especially suitable for manufacturing high-frequency components such as microwave dielectric resonators, satellite filters and the like.
The current medium dielectric constant microwave dielectric ceramic really forms into commercial BaMg 1/3 Ta 2/3 O 3 （BMT）、BaZn 1/ 3 Ta 2/3 O 3 （BZT）、Ba（Co，Zn） 1/3 Nb 2/3 O 3 (BCZN) and CaTiO 3 -NdAlO 3 The system is the main. On one hand, ta is expensive and limits the application of Ta, and on the other hand, the quality factor QF of the dielectric ceramic materials can only reach about 40000GHz usually, so that the requirement of modern communication is difficult to meet.
Disclosure of Invention
The invention aims to provide a microwave dielectric ceramic material with a medium dielectric constant and a preparation method thereof, so as to obtain the microwave dielectric ceramic material with high QF and a dielectric constant of about 45.
According to one aspect of the present invention, there is provided a microwave dielectric ceramic material with a medium dielectric constant: the chemical composition of the compound is xCa (1－m) M m X n Ti （1－n） O 3 -yLaAlO 3 (ii) a M comprises at least one of magnesium element, barium element and strontium element; x comprises Zn element and at least one of vanadium subgroup element; x + y =1.
The invention uses CaTiO 3 -LaAlO 3 Based on Sr, mg, ba to CaTiO 3 Ca in the solution is substituted, and Zn and vanadium subgroup elements are used for replacing CaTiO 3 Substituted with Ti in (1), and the resulting substituent is reacted with LaAlO 3 The solid solution is prepared according to a certain proportion, so that the ceramic material with good microwave performance is obtained, the dielectric constant of the ceramic material is continuously adjustable and stably distributed, the dielectric constant of the ceramic material can reach about 45, the ceramic material also has a high-level QF value, and the temperature frequency coefficient is stable at different temperatures. On the other hand, compared with the current general microwave dielectric ceramic with medium dielectric constant, the microwave dielectric ceramic material provided by the invention still has good microwave performance under the condition of reducing the use of expensive raw materials as much as possible, thereby effectively reducing the cost for preparing the microwave dielectric ceramic material with medium dielectric constant, obviously improving the economic benefit of the microwave dielectric ceramic material and being beneficial to popularization and application of the microwave dielectric ceramic material with medium dielectric constant.
Preferably, M comprises Sr element, and the stoichiometric ratio of Sr element to Ca element in the chemical composition of the microwave dielectric ceramic material is not lower than 1.
Preferably, in the chemical composition of the microwave dielectric ceramic material, the stoichiometric ratio of Sr element to Ca element is not higher than 1.
Preferably, in the chemical composition of the microwave dielectric ceramic material, the stoichiometric ratio of Sr element to Ca element is 1.5.
In CaTiO 3 -LaAlO 3 In the system, sr is used for CaTiO 3 When the stoichiometric ratio of Sr element and Ca element is in the above-mentioned limited range, the dielectric constant of the obtained microwave dielectric ceramic material is basically close to 45, so that it is specially suitable for making high-frequency components of microwave dielectric resonator and satellite filter, etc.
Preferably, the vanadium subgroup element in X comprises Nb element, and the stoichiometric ratio of Nb element to Zn element in the chemical composition of the microwave dielectric ceramic material is not lower than 1.
Preferably, in the chemical composition of the microwave dielectric ceramic material, the stoichiometric ratio of the Nb element to the Zn element is 2.
In CaTiO 3 -LaAlO 3 In the system, zn and Nb are opposite to CaTiO 3 When the stoichiometric ratio of Nb element and Zn element is in the above-mentioned limited range, the QF value of the obtained microwave dielectric ceramic material is up to above 75000, and it has good product quality.
Preferably, in the chemical composition of the microwave dielectric ceramic material, the ratio of x to y is not lower than 1.
According to another aspect of the present invention, there is provided a method for preparing the microwave dielectric ceramic material with medium dielectric constant, which is characterized by: including Ca (1－m) M m X n Ti （1－n） O 3 A synthesis process and a target product synthesis process; in Ca (1－m) M m X n Ti （1－n） O 3 The synthesis process comprises the following steps: s1, preparing materials according to the chemical composition of a target product, wherein the required raw materials comprise an alkaline earth metal element compound, a zinc-containing compound, a vanadium subgroup element compound and a titanium-containing compound; s2, prefabricating a zinc-containing compound and a vanadium subgroup element compound to obtain ZnNb 2 O 6 A precursor; s3, znNb is adopted 2 O 6 Ca synthesis from precursor, alkaline earth metal element compound and titanium-containing compound (1－m) M m X n Ti （1－n） O 3 (ii) a The synthesis process of the target product comprises the following steps: according to the target productChemical composition of the material, weighing Ca according to the amount (1－m) M m X n Ti （1－n） O 3 And LaAlO 3 And synthesizing a target product.
Preferably, in Ca (1－m) M m X n Ti （1－n） O 3 In the synthesis process, znNb is prefabricated 2 O 6 The precursor comprises the following steps: mixing a zinc-containing compound and a vanadium subgroup element compound to form a mixture I, and calcining the mixture I at the temperature of 800-1100 ℃ for 1.5-3 hours.
Preferably, the mixture I is subjected to ball milling for 3 to 6 hours before being calcined.
Preferably, in Ca (1－m) M m X n Ti （1－n） O 3 In the synthesis process: ca (1－m) M m X n Ti （1－n） O 3 The synthesis conditions of (A) are to adopt ZnNb 2 O 6 Mixing the precursor and the rest raw materials to form a mixture II, and calcining the mixture II at the temperature of 900-1300 ℃ for 1-3 hours.
Preferably, before calcining the mixture II, performing ball milling treatment on the mixture II, wherein the ball milling time is not less than 16 hours.
Preferably, during synthesis of the target product: will include Ca (1－m) M m X n Ti （1－n） O 3 And LaAlO 3 Sintering the mixed material at 1400 to 1650 ℃ to form a solid solution, thereby preparing the target product.
Preferably, laAlO 3 The preparation method comprises the following steps: according to LaAlO 3 Weighing a lanthanum-containing compound and an aluminum-containing compound according to the stoichiometric ratio of the La element to the Al element, mixing the lanthanum-containing compound and the aluminum-containing compound to form a mixture IV, and calcining the mixture IV at the temperature of 1000-1300 ℃ for 1-3 hours.
Preferably, the synthesis process of the target product specifically comprises the following steps: a. ca is quantitatively added according to the chemical composition of the target product (1－m) M m X n Ti （1－n） O 3 And LaAlO 3 Mixing and adding a binder thereto, thereby forming a mixture iii; b. pressing the mixture III into a green body, and heating the green body to discharge glue; c. heating the product obtained in the step b after glue discharging at a heating speed of 10 to 30 ℃/min to 1400 to 1650 ℃, and preserving heat for 2 to 4 hours to obtain a target product.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Example 1
1. Preparation of Ca 0.85 Sr 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 -LaAlO 3
In this embodiment, electronic grade strontium carbonate, calcium carbonate, zinc oxide, niobium pentoxide, titanium dioxide, lanthanum trioxide, and aluminum oxide are used as raw materials to prepare a microwave dielectric ceramic material, and the preparation process includes Ca 0.85 Sr 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 Synthesis Process, laAlO 3 A synthetic process and a target product synthetic process.
Ca 0.85 Sr 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 The specific operation of the synthesis process is as follows:
s1, accurately weighing 55.89g of zinc oxide, 875.43g of calcium carbonate, 228.04g of strontium carbonate, 658.13g of titanium dioxide and 182.52g of niobium pentoxide by using an analytical balance;
s2, mixing zinc oxide and niobium pentoxide, marking the obtained mixture as a mixture I, performing ball milling on the mixture I for 4 hours, and calcining the ball-milled mixture I at the calcining temperature of 1000 ℃ for 2 hours to form ZnNb 2 O 6 Precursor powder;
s3, carrying out ZnNb preparation 2 O 6 Mixing the precursor powder with calcium carbonate, strontium carbonate and titanium dioxide, marking the obtained mixture as a mixture II, carrying out ball milling on the mixture II for 20 hours, sequentially drying and crushing the ball-milled mixture II, and calcining the obtained material at 1160 ℃ for 2 hours to obtain Ca 0.85 Sr 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 。
LaAlO 3 The specific operation of the synthesis process is as follows:
1522.81g of lanthanum sesquioxide and 477.19g of alumina are accurately weighed by an analytical balance, a mixture formed by mixing the lanthanum sesquioxide and the alumina is marked as a mixture IV, the mixture IV is ball-milled for 20 hours, then the mixture IV is introduced into a sand mill for treatment for 25 minutes, the treated mixture IV is sequentially dried and crushed, and then the obtained material is calcined for 2 hours at 1200 ℃, thus obtaining LaAlO 3 。
The specific operation of the target product synthesis process is as follows:
a. the Ca prepared in this example was quantitatively determined according to the chemical composition of the target product 0.85 Sr 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 And LaAlO 3 Mixing, performing ball milling for 20 hours, and adding 2% of PVA (polyvinyl alcohol) binder into the ball-milled materials according to the mass percentage to form a mixture III;
b. granulating the mixture III, dry-pressing and molding in a molding die under the pressure of 60Mpa to prepare a cylindrical green body with the diameter of 15mm and the height of 7.5mm, and calcining the green body in a tunnel kiln at the temperature of 600 ℃ for 2 hours to remove rubber;
c. and c, heating the product obtained in the step b after the glue is discharged at a heating speed of 10 ℃/min, heating to 1600 ℃, preserving the heat for 2.5 hours, and naturally cooling to obtain the target product.
The chemical composition of the target product prepared by the method is xCa 0.85 Sr 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 Wherein x + y =1.
2. Performance testing
Testing xCa at 4-9GHz frequency by adopting Agilent network analyzer 0.85 Sr 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 The dielectric properties of (2). Samples with different proportions are randomly extracted by 5 pieces to measure the microwave performance, and the test results are shown in table 1. As shown in Table 1, xCa was prepared in this example 0.85 Sr 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 The dielectric constant is continuously adjustable and stably distributed, the microwave dielectric ceramic material with the dielectric constant about 45 can be obtained, the QF value can reach more than 75000, some components can even reach more than 80000, and the temperature frequency coefficients at different temperatures are stable.
TABLE 1 xCa 0.85 Sr 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 Microwave performance
Example 2
1. Preparation of Ca 0.85 Mg 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 -LaAlO 3
In this example, electronic-grade magnesium oxide, calcium carbonate, zinc oxide, niobium pentoxide (Nb 2O 5), titanium dioxide, lanthanum trioxide, and aluminum oxide are used as raw materials to prepare a microwave dielectric ceramic material, and the preparation process is Ca 0.85 Sr 0.15 （Zn 1/ 3 Nb 2/3 ） 0.2 Ti 0.8 O 3 Synthesis Process, laAlO 3 A synthesis process and a target product synthesis process.
Ca 0.85 Mg 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 The specific operation of the synthesis process is as follows:
s1, accurately weighing 55.89g of zinc oxide, 875.43g of calcium carbonate, 62.27g of magnesium oxide, 658.13g of titanium dioxide and 182.52g of niobium pentoxide by using an analytical balance;
s2, mixing zinc oxide and niobium pentoxide, marking the obtained mixture as a mixture I, performing ball milling on the mixture I for 4 hours, and calcining the ball-milled mixture I at the calcining temperature of 1000 ℃ for 2 hours to form ZnNb 2 O 6 Precursor powder;
s3, carrying out ZnNb preparation 2 O 6 Mixing the precursor powder with calcium carbonate, magnesium oxide and titanium dioxide, marking the obtained mixture as a mixture II, carrying out ball milling on the mixture II for 20 hours, sequentially drying and crushing the ball-milled mixture II, and calcining the obtained material at 1150 ℃ for 2 hours to obtain Ca 0.85 Mg 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 。
LaAlO 3 The specific operation of the synthesis process is as follows:
1522.81g of lanthanum trioxide and 477.19g of alumina are accurately weighed by an analytical balance, a mixture formed by mixing the lanthanum trioxide and the alumina is marked as a mixture IV, the mixture IV is subjected to ball milling for 20 hours, the ball-milled mixture IV is sequentially dried and crushed, and the obtained material is calcined for 2 hours at 1200 ℃ to prepare LaAlO 3 。
The specific operation of the target product synthesis process is as follows:
a. ca prepared in this example was quantitatively determined according to the chemical composition of the target product 0.85 Sr 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 And LaAlO 3 Mixing, ball milling for 20 hr, treating in a sand mill for 25 min, and adding PVA binder in 2 wt% into the treated material to formForming a mixture III;
b. granulating the mixture III, dry-pressing and molding in a molding die under the pressure of 60Mpa to prepare a cylindrical green body with the diameter of 15mm and the height of 7.5mm, and calcining the green body in a tunnel kiln at the temperature of 600 ℃ for 2 hours to remove rubber;
c. heating the product obtained in the step b after the glue discharging at the heating rate of 10 ℃/min, heating to 1450 ℃, preserving the temperature for 2.5 hours, and naturally cooling to obtain the target product.
The chemical composition of the target product prepared by the method is xCa 0.85 Mg 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 Wherein x + y =1.
2. Performance test
Testing xCa at 4-9GHz frequency by using Agilent network analyzer 0.85 Mg 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 The dielectric properties of (2). 5 samples with different proportions are randomly extracted to measure the microwave performance, and the test results are shown in table 2. As shown in Table 2, xCa was prepared in this example 0.85 Mg 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 The dielectric constant of the material is continuously adjustable and stably distributed, the QF value of the material can reach more than 60000, and the temperature frequency coefficients at different temperatures are stable.
TABLE 2 xCa 0.85 Mg 0.15 （Zn 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 Microwave performance
Example 3
1. Preparation of Ca 0.85 Sr 0.15 （Zn 1/3 V 2/3 ） 0.2 Ti 0.8 O 3 -LaAlO 3
In this example, electronic grade strontium carbonate, calcium carbonate and zinc oxide were usedVanadium pentoxide, titanium dioxide, lanthanum trioxide and aluminum oxide are used as raw materials to prepare the microwave dielectric ceramic material, and the preparation process is Ca 0.85 Sr 0.15 （Zn 1/3 V 2/3 ） 0.2 Ti 0.8 O 3 Synthesis Process, laAlO 3 A synthetic process and a target product synthetic process.
Ca 0.85 Sr 0.15 （Zn 1/3 V 2/3 ） 0.2 Ti 0.8 O 3 The specific operation of the synthesis process is as follows:
s1, accurately weighing 55.89g of zinc oxide, 875.43g of calcium carbonate, 228.04g of strontium carbonate, 658.13g of titanium dioxide and 124.95g of vanadium pentoxide by using an analytical balance;
s2, mixing zinc oxide and vanadium pentoxide, marking the obtained mixture as a mixture I, carrying out ball milling on the mixture I for 4 hours, and then calcining the ball-milled mixture I at the calcining temperature of 1000 ℃ for 2 hours to form ZnV 2 O 6 Precursor powder;
s3, preparing the ZnV 2 O 6 Mixing the precursor powder with calcium carbonate, strontium carbonate and titanium dioxide, marking the obtained mixture as a mixture II, carrying out ball milling on the mixture II for 20 hours, sequentially drying and crushing the ball-milled mixture II, and calcining the obtained material at 1160 ℃ for 2 hours to obtain Ca 0.85 Sr 0.15 （Zn 1/3 V 2/3 ） 0.2 Ti 0.8 O 3 。
LaAlO 3 The specific operation of the synthesis process is as follows:
1522.81g of lanthanum sesquioxide and 477.19g of alumina are accurately weighed by an analytical balance, a mixture formed by mixing the lanthanum sesquioxide and the alumina is marked as a mixture IV, the mixture IV is ball-milled for 20 hours, then the mixture IV is introduced into a sand mill for treatment for 25 minutes, the treated mixture IV is sequentially dried and crushed, and then the obtained material is calcined for 2 hours at 1200 ℃, thus obtaining LaAlO 3 。
The specific operation of the target product synthesis process is as follows:
a. the Ca prepared in this example was quantitatively determined according to the chemical composition of the target product 0.85 Sr 0.15 （Zn 1/3 V 2/3 ） 0.2 Ti 0.8 O 3 And LaAlO 3 Mixing, performing ball milling for 20 hours, and adding 2% of PVA (polyvinyl alcohol) binder into the ball-milled materials according to the mass percentage to form a mixture III;
b. granulating the mixture III, dry-pressing and molding in a molding die under the pressure of 60Mpa to prepare a cylindrical green body with the diameter of 15mm and the height of 7.5mm, and calcining the green body in a tunnel kiln at the temperature of 600 ℃ for 2 hours to remove rubber;
c. and c, heating the product obtained in the step b after the glue is discharged at a heating speed of 10 ℃/min, heating to 1600 ℃, preserving the heat for 2.5 hours, and naturally cooling to obtain the target product.
The chemical composition of the target product prepared by the method is xCa 0.85 Sr 0.15 （Zn 1/3 V 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 Wherein x + y =1.
2. Performance test
Testing xCa at 4-9GHz frequency by using Agilent network analyzer 0.85 Sr 0.15 （Zn 1/3 V 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 The dielectric properties of (2). 5 samples with different proportions are randomly extracted to measure the microwave performance, and the test results are shown in Table 3. As shown in Table 3, xCa was prepared in this example 0.85 Sr 0.15 （Zn 1/3 V 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 The dielectric constant of the material is continuously adjustable and stably distributed, the QF value can reach more than 70000, and the temperature frequency coefficients at different temperatures are stable.
TABLE 3 xCa 0.85 Sr 0.15 （Zn 1/3 V 2/3 ） 0.2 Ti 0.8 O 3 -yLaAlO 3 Microwave performance
Comparative example 1
Treatment I
1. Preparation of xCa 0.85 Sr 0.15 TiO 3 -yLaAlO 3 Microwave dielectric ceramic material
The raw materials adopted in this embodiment are electronic grade strontium carbonate, calcium carbonate, titanium dioxide, lanthanum oxide and aluminum oxide, and the microwave dielectric ceramic material is prepared according to the following steps:
the method comprises the following steps: accurately weighing 228.04g of strontium carbonate, 875.43g of calcium carbonate and 822.19g of titanium dioxide by using an analytical balance, ball-milling and mixing the mixture for 20 hours, drying, crushing and calcining at 1100 ℃ for 2 hours to obtain Sr-substituted CaTiO 3 Ca derived from Ca in (1) 0.9 Sr 0.1 TiO 3 ；
Step two: 1522.81g of lanthanum sesquioxide and 477.19g of alumina are accurately weighed by an analytical balance, a mixture formed by mixing the lanthanum sesquioxide and the alumina is marked as a mixture IV, the mixture IV is ball-milled for 20 hours, then the mixture IV is introduced into a sand mill for treatment for 25 minutes, the treated mixture IV is sequentially dried and crushed, and then the obtained material is calcined for 2 hours at 1200 ℃, thus obtaining LaAlO 3 ；
Step three: adding Ca 0.9 Sr 0.1 TiO 3 And LaAlO 3 According to the proportion (Ca) 0.9 Sr 0.1 TiO 3 : LaAlO 3 Y), ball milling for 20 hours again, then introducing into a sand mill for treatment for 30 minutes, after uniform mixing, adding 2% of PVA binder for spray granulation, and dry-pressing in a forming die under the pressure of 60MPa to prepare a cylindrical green body with the diameter of 15mm and the height of 7.5 mm;
step four: discharging the glue of the green body prepared in the third step in a tunnel kiln at 600 ℃ for 2 hours, then heating to 1480 ℃ at the speed of 10 ℃/min, preserving the heat for 2.5 hours, and naturally cooling to obtain xCa 0.9 Sr 0.1 TiO 3 -yLaAlO 3 Microwave ovenA sample of dielectric ceramic material.
2. Performance testing
Testing xCa at 4-9GHz frequency by using Agilent network analyzer 0.85 Sr 0.15 TiO 3 -yLaAlO 3 The dielectric properties of (2). The microwave performance of samples with different ratios was measured by randomly taking 5 samples, and the results are shown in table 4. According to Table 4,xCa 0.9 Sr 0.1 TiO 3 -yLaAlO 3 The microwave ceramic has a stable and continuously adjustable dielectric constant distribution and stable temperature frequency coefficients at different temperatures, but the dielectric constant of the microwave ceramic is basically distributed around 35, and the QF value of the microwave ceramic is basically not more than 50000.
TABLE 4 xCa 0.85 Sr 0.15 TiO 3 -yLaAlO 3 Microwave performance
Treatment II
1. Preparation of xCa (Zn) 1/3 Nb 2/3 ) 0.2 Ti 0.8 O 3 -yLaAlO 3 Microwave dielectric ceramic
The raw materials adopted in this embodiment are electronic grade zinc oxide, niobium pentoxide, calcium carbonate, titanium dioxide, lanthanum trioxide, and alumina, and the microwave dielectric ceramic material is prepared according to the following steps:
step one, accurately weighing 55.89g of zinc oxide, 1030.53g of calcium carbonate, 658.13g of titanium dioxide and 182.52g of niobium pentoxide by using an analytical balance, ball-milling and mixing the mixture for 20 hours, drying, crushing and calcining at 1160 ℃ for 2 hours to obtain CaTiO jointly substituted by Zn and Nb 3 Ca (Zn) derived from Ti in (1) 1/3 Nb 2/3 ) 0.2 Ti 0.8 O 3 ；
Secondly, 1522.81g of lanthanum sesquioxide and 477.19g of alumina are accurately weighed by an analytical balance, a mixture formed by mixing the lanthanum sesquioxide and the alumina is marked as a mixture IV, the mixture IV is ball-milled for 20 hours, then the mixture IV is introduced into a sand mill for treatment for 25 minutes, and the treated mixture is treatedThe mixture IV is dried and crushed in sequence, and then the obtained material is calcined for 2 hours at 1200 ℃ to prepare LaAlO 3 ；
Step three, adding Ca (Zn) 1/3 Nb 2/3 ) 0.2 Ti 0.8 O 3 And LaAlO 3 According to the proportion (Ca (Zn) 1/3 Nb 2/3 ） 0.2 Ti 0.8 O 3 :LaAlO 3 Y), ball milling for 20 hours again, then introducing into a sand mill for processing for 30 minutes, after mixing uniformly, adding 2% of PVA binder for spray granulation, and dry-pressing in a forming die under the pressure of 60MPa to prepare a cylindrical green body with the diameter of 15mm and the height of 7.5 mm;
step four, discharging glue at 600 ℃ for 2 hours in a tunnel kiln, heating to 1600 ℃ at the speed of 10 ℃/min, preserving heat for 2.5 hours, and naturally cooling to obtain xCa (Zn) 1/3 Nb 2/3 ) 0.2 Ti 0.8 O 3 -yLaAlO 3 Microwave dielectric ceramic material samples.
2. Performance testing
Testing xCa (Zn) at 4-9GHz frequency by using Agilent network analyzer 1/3 Nb 2/3 ) 0.2 Ti 0.8 O 3 -yLaAlO 3 The dielectric properties of (2). Samples of different proportions were randomly sampled for 5 pieces to measure their microwave properties, and the results are shown in Table 5. According to Table 5, xCa (Zn) 1/3 Nb 2/3 ) 0.2 Ti 0.8 O 3 -yLaAlO 3 The dielectric constant of the microwave dielectric ceramic is continuously adjustable and stably distributed, the QF value can reach more than 75000, however, the temperature frequency coefficient stability of the prepared microwave dielectric ceramic dielectric at different temperatures is poor, and the absolute value of the temperature frequency coefficient of certain products reaches more than 10 ppm/DEG C.
TABLE 5 xCa (Zn) 1/3 Nb 2/3 ) 0.2 Ti 0.8 O 3 -yLaAlO 3 Microwave performance
This implementationExample by setting treatment I and treatment II to the Ca obtained in example 1 0.85 Sr 0.15 （Zn 1/ 3 Nb 2/3 ） 0.2 Ti 0.8 O 3 -LaAlO 3 Microwave dielectric ceramic material composition contrast with CaTiO 3 -LaAlO 3 Based on the system, only Sr is used for CaTiO 3 The Ca in the microwave dielectric ceramic material is subjected to single element substitution, the dielectric constant and QF of the obtained microwave dielectric ceramic material are low, and only Zn and Nb are used for CaTiO 3 The Ti in the microwave dielectric ceramic material is replaced by double elements, and the obtained microwave dielectric ceramic material has poor product performance stability and is difficult to meet the requirement of batch production. In conclusion, sr, zn and Nb are simultaneously adopted for CaTiO 3 -LaAlO 3 CaTiO in the System 3 Can remarkably optimize CaTiO by doping 3 -LaAlO 3 The microwave medium ceramic material can be CaTiO 3 -LaAlO 3 The system has medium dielectric constant, high QF value and stable temperature frequency coefficient.
Comparative example 2
In this example, sr, zn, nb doped xCaTiO is prepared from electronic grade strontium carbonate, calcium carbonate, zinc oxide, niobium pentoxide, titanium dioxide, lanthanum trioxide, and aluminum oxide 3 -yLaAlO 3 The microwave dielectric ceramic material is prepared by the following steps:
CaTiO doped with Sr, zn and Nb 3 The preparation of (1):
s1, accurately weighing 55.89g of zinc oxide, 875.43g of calcium carbonate, 228.04g of strontium carbonate, 658.13g of titanium dioxide and 182.52g of niobium pentoxide by using an analytical balance;
s2, mixing the materials, carrying out ball milling on the mixed materials for 20 hours, drying and crushing the ball-milled materials in sequence, calcining the obtained materials at 1160 ℃ for 2 hours, and naturally cooling to room temperature to obtain doped CaTiO 3 。
LaAlO 3 The specific operation of the synthesis process is as follows:
1522.81g of lanthanum trioxide and 477.19g of alumina are accurately weighed by an analytical balance, and the lanthanum trioxide is addedThe mixture mixed with the alumina is marked as a mixture IV, the mixture IV is ball-milled for 20 hours, then the mixture IV is introduced into a sand mill to be treated for 25 minutes, the treated mixture IV is sequentially dried and crushed, and then the obtained material is calcined for 2 hours at 1200 ℃ to prepare LaAlO 3 。
The specific operation of the target product synthesis process is as follows:
a. the doped CaTiO prepared in this example was dosed according to the chemical composition of the target product 3 And LaAlO 3 Mixing, performing ball milling for 20 hours, and adding 2% of PVA (polyvinyl alcohol) binder into the ball-milled materials according to the mass percentage to form a mixture III;
b. granulating the mixture III, dry-pressing and molding in a molding die under the pressure of 60Mpa to prepare a cylindrical green body with the diameter of 15mm and the height of 7.5mm, and calcining the green body in a tunnel kiln at the temperature of 600 ℃ for 2 hours to remove rubber;
c. and (c) heating the product obtained in the step (b) after the glue is discharged at the heating rate of 10 ℃/min, heating to 1600 ℃, preserving the heat for 2.5 hours, and naturally cooling to obtain the finished microwave dielectric ceramic material.
The dielectric properties of the product prepared in this example were tested at 4-9GHz frequency using an agilent network analyzer. The microwave performance of samples with different ratios was measured by randomly taking 5 samples, and the results are shown in table 6. The types of the raw materials and the feeding amounts of the raw materials used in this example are all the same as those in example 1, and compared with the preparation scheme of the microwave dielectric ceramic material provided in example 1, znNb is not prefabricated in this example 2 O 6 The precursor is directly mixed and calcined for synthesizing the microwave dielectric ceramic material at one time, in the step of lacking the prefabricated precursor, zn may enter the microwave dielectric ceramic material system in the form of Ca in a substitution system, and Zn cannot be guaranteed to be substituted only by Ti in the system, so that the quality of the prepared microwave dielectric ceramic material is unstable, which is reflected by larger absolute value of temperature frequency coefficient and lower QF value。
TABLE 6 microwave Properties of microwave dielectric ceramic Material obtained in this example
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the present invention.
Claims (8)
1. A microwave dielectric ceramic material with a medium dielectric constant, which is characterized in that:
the chemical composition of the compound is xCa (1－m) M m X n Ti （1－n） O 3 -yLaAlO 3 ；
M comprises Sr element, and the stoichiometric ratio of Sr element to Ca element in the chemical composition of the microwave dielectric ceramic material is not lower than 1; x comprises Zn and also comprises a vanadium subgroup element, wherein the vanadium subgroup element comprises Nb, and the stoichiometric ratio of the Nb element to the Zn element in the chemical composition of the microwave dielectric ceramic material is not less than 1; x + y =1;
the preparation method of the microwave dielectric ceramic material comprises Ca (1－m) M m X n Ti （1－n） O 3 A synthesis process and a target product synthesis process; in the Ca (1－m) M m X n Ti （1－n） O 3 The synthesis process comprises the following steps: s1, preparing materials according to the chemical composition of a target product, wherein the required raw materials comprise an alkaline earth metal element compound, a zinc-containing compound, a vanadium subgroup element compound and a titanium-containing compound; s2, prefabricating the zinc-containing compound and the vanadium secondary group element compound to obtain ZnNb 2 O 6 A precursor; s3, adopting the ZnNb 2 O 6 Ca is synthesized by the precursor, the alkaline earth metal element compound and the titanium-containing compound (1－m) M m X n Ti （1－n） O 3 (ii) a The synthesis process of the target product comprises the following steps: weighing the Ca according to the chemical composition of the target product (1－m) M m X n Ti （1－n） O 3 And LaAlO 3 And synthesizing the target product.
2. A microwave dielectric ceramic material of medium dielectric constant as claimed in claim 1, wherein: in the chemical composition of the microwave dielectric ceramic material, the ratio of x to y is not lower than 1.
3. A method for preparing a dielectric constant microwave dielectric ceramic material as claimed in any one of claims 1 or 2, wherein:
including Ca (1－m) M m X n Ti （1－n） O 3 A synthesis process and a target product synthesis process;
in the Ca (1－m) M m X n Ti （1－n） O 3 The synthesis process comprises the following steps:
s1, preparing materials according to the chemical composition of a target product, wherein the required raw materials comprise an alkaline earth metal element compound, a zinc-containing compound, a vanadium subgroup element compound and a titanium-containing compound;
s2, prefabricating the zinc-containing compound and the vanadium secondary group element compound to obtain ZnNb 2 O 6 A precursor;
s3, adopting the ZnNb 2 O 6 Synthesizing Ca by the precursor and the rest raw materials (1－m) M m X n Ti （1－n） O 3 ；
The synthesis process of the target product comprises the following steps: weighing the Ca according to the chemical composition of the target product (1－m) M m X n Ti （1－n） O 3 And LaAlO 3 And synthesizing the target product.
4. The method of claim 3, wherein said step of applying is performed in a batch processCa (1－m) M m X n Ti （1－n） O 3 In the synthesis process, the ZnNb is prefabricated 2 O 6 The precursor comprises the following steps: mixing the zinc-containing compound and the vanadium subgroup element compound to form a mixture I, and calcining the mixture I at the temperature of 800-1100 ℃ for 1.5-3 hours.
5. The method of claim 4, wherein: before the mixture I is calcined, performing ball milling treatment on the mixture I, wherein the ball milling time is 3-6 hours.
6. The method of claim 3, wherein Ca is present in (1－m) M m X n Ti （1－n） O 3 In the synthesis process: the Ca (1－m) M m X n Ti （1－n） O 3 Under the synthesis conditions that the ZnNb is adopted 2 O 6 Mixing the precursor and the rest of the raw materials to form a mixture II, and calcining the mixture II at the temperature of 900-1300 ℃ for 1-3 hours.
7. The method of claim 3, wherein during the synthesis of the target product: will comprise the Ca (1－m) M m X n Ti （1－n） O 3 And LaAlO 3 Sintering the mixed material at 1400 to 1650 ℃ to form a solid solution, thereby preparing the target product.
8. The method of claim 7, wherein the target product synthesis process specifically comprises the following steps:
a. quantitatively adding the Ca according to the chemical composition of the target product (1－m) M m X n Ti （1－n） O 3 And LaAlO 3 Mixing and adding a binder thereto, thereby forming a mixture iii;
b. pressing the mixture III into a green body, and heating the green body to discharge rubber;
c. heating the product obtained in the step b after glue discharging at a heating rate of 10-30 ℃/min, heating to 1400-1650 ℃, and preserving heat for 2-4 hours to obtain the target product.
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