CN109761603B - BCSLTM-SA composite microwave dielectric ceramic and preparation method thereof - Google Patents
BCSLTM-SA composite microwave dielectric ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention provides BCSLTM-SA composite microwave dielectric ceramic and a preparation method thereof, wherein the BCSLTM-SA composite microwave dielectric ceramic comprises the following components: BCSLTM and SmAlO3(ii) a Wherein the SmAlO is3The mass percentage of the component (A) is 5-15%. Compared with the prior art, the BCSLTM-SA composite microwave dielectric ceramic provided by the invention is compounded by BCSLTM and SA in a specific ratio; the BCSLTM-SA composite microwave dielectric ceramic comprises BCSLTM and SmAlO3The two crystal phase structures have stable structures, specific dielectric constants and higher Q multiplied by f values, and simultaneously the temperature coefficient of the resonant frequency is continuously adjustable.
Description
Technical Field
The invention relates to the technical field of microwave dielectric ceramics, in particular to BCSLTM-SA composite microwave dielectric ceramics and a preparation method thereof.
Background
With the continuous development of modern communication technology, the requirements for miniaturization, high performance and low cost of mobile communication equipment are higher and higher, and the trend depends on the dielectric constant of the microwave dielectric ceramic material. The larger the dielectric constant and the smaller the wavelength at the same resonance frequency, the smaller the size of the corresponding dielectric resonator. Meanwhile, the electromagnetic energy is more concentrated in the medium when the dielectric constant is larger, and the influence of the surrounding environment is smaller. Therefore, the high-dielectric-constant microwave dielectric ceramic material (with the dielectric constant of 55-90) is beneficial to miniaturization of equipment and high performance.
However, many Ba compounds having a dielectric constant of about 80 have been studied6-3xLn8+2xTi18O54The (Ln ═ La, Sm) system has a large loss, is unstable in structure, and is liable to cause titanium reduction at a high sintering temperature, leading to a significant deterioration in performance. Therefore, it is urgent to develop a microwave dielectric ceramic material having a high Q value of 55 to 80 in dielectric constant.
Disclosure of Invention
In view of the above, the invention aims to provide a BCSLTM-SA composite microwave dielectric ceramic and a preparation method thereof, and the BCSLTM-SA composite microwave dielectric ceramic provided by the invention has the advantages that the dielectric constant is 56-68, the dielectric loss is low, and the temperature coefficient of the resonant frequency is continuously adjustable.
The invention provides BCSLTM-SA composite microwave dielectric ceramic, which comprises the following components:
BCSLTM and SmAlO3；
Wherein the SmAlO is3The mass percentage of the component (A) is 5-15%.
Preferably, the method further comprises the following steps:
an additive;
the additive is prepared from the following components in percentage by mass (40-55): (25-35): (15-30): (2-10): (1-10) SiO2、B2O3、Al2O3ZnO and MgO.
Preferably, the preparation method of the additive specifically comprises the following steps:
mixing SiO2、B2O3、Al2O3And ZnO and MgO are mixed and ball-milled, then melted for 10min to 30min at 1200 ℃ to 1300 ℃, and then crushed and sieved after separation to obtain the additive.
The invention also provides a preparation method of the BCSLTM-SA composite microwave dielectric ceramic, which comprises the following steps:
a) mixing BaCO3、CaCO3、Sm2O3、La2O3、TiO2And MnO2After mixing, carrying out primary grinding treatment, and then carrying out primary presintering to obtain a BCSLTM presintering material; simultaneously, Sm is added2O3And Al2O3After mixing, carrying out secondary grinding treatment, and then carrying out secondary pre-sintering to obtain an SA pre-sintering material;
b) mixing the BCSLTM pre-sintering material and the SA pre-sintering material obtained in the step a), and then grinding for the third time to obtain powder; adding an adhesive into the powder for granulation molding to obtain a ceramic green body; and finally, sintering the obtained ceramic green body to obtain the BCSLTM-SA composite microwave dielectric ceramic.
Preferably, the first grinding treatment in step a) specifically comprises the following steps:
mixing the mixed raw materials, zirconium balls and water in a ratio of 1: (1.5-2.5): (1.5-2.5), ball-milling for 6-10 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain the mixed material after the first grinding treatment.
Preferably, the temperature of the first presintering in the step a) is 800-1100 ℃, the heating rate is 2.5-3.5 ℃/min, and the heat preservation time is 2-3 h.
Preferably, the adhesive in the step b) is a polyvinyl alcohol aqueous solution with the mass percentage of 6-8%;
the mass ratio of the powder to the adhesive is 100: (7-10).
Preferably, the granulation molding process in the step b) specifically comprises the following steps:
adding an adhesive into the powder, granulating and grinding for 0.5-1.5 h, sieving with a 70-90 mesh sieve, and pressing and molding the obtained powder under the pressure of 80-120 MPa to obtain the ceramic green body.
Preferably, the sintering temperature in the step b) is 1000-1100 ℃, the heating rate is 2.5-3.5 ℃/min, and the heat preservation time is 2-4 h.
Preferably, the step b) further comprises:
and mixing the obtained BCSLTM pre-sintered material and SA pre-sintered material with additives, and then grinding for the third time to obtain powder.
The invention provides BCSLTM-SA composite microwave dielectric ceramic and a preparation method thereof, wherein the BCSLTM-SA composite microwave dielectric ceramic comprises the following components: BCSLTM and SmAlO3(ii) a Wherein the SmAlO is3The mass percentage of the component (A) is 5-15%. Compared with the prior art, the BCSLTM-SA composite microwave dielectric ceramic provided by the invention consists of BCSLTM and SA (SmAlO) in a specific ratio3) Wherein BCSLTM is compounded with BaCO3、CaCO3、Sm2O3、La2O3、TiO2And MnO2Is compounded with Sm as basic material and Sm as SA2O3And Al2O3Is compounded by basic raw materials; the BCThe SLTM-SA composite microwave dielectric ceramic comprises BCSLTM and SmAlO3The two crystal phase structures not only lead the resonance frequency temperature coefficient of the microwave dielectric ceramic after being compounded to approach zero, but also improve the Q multiplied by f value of the ceramic; meanwhile, a small amount of Mn replaces Ti and is mainly used as an acceptor for doping, on one hand, the radius of Mn atoms is slightly larger than that of Ti, the addition of Mn can stabilize the space structure and improve the Qxf value, and on the other hand, the valence change of Mn is utilized in the sintering process to inhibit the reduction of Ti and further improve the Qxf value. The BCSLTM-SA composite microwave dielectric ceramic provided by the invention has a stable structure, a specific dielectric constant and a high Q multiplied by f value, and the temperature coefficient of the resonant frequency is continuously adjustable. Experimental results show that the dielectric constant of the BCSLTM-SA composite microwave dielectric ceramic is 56-68, the Qxf value is 20432 GHz-29279 GHz, and compared with other systems of microwave dielectric ceramics with the same dielectric constant, the system has the advantages of large Qxf value and low dielectric loss; meanwhile, the temperature coefficient of the resonance frequency is continuously adjustable between-5 ppm/DEG C and +5 ppm/DEG C, and the formula can be flexibly adjusted.
In addition, the preparation method provided by the invention is simple, the sintering temperature is low, only 1000-1100 ℃, and the cost is low; and the method meets the requirement of environmental protection, has no toxicity and no pollution to the environment, is suitable for large-scale industrialization, and has very wide development prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides BCSLTM-SA composite microwave dielectric ceramic, which comprises the following components:
BCSLTM and SmAlO3；
Wherein the SmAlO is3The mass percentage of the component (A) is 5-15%.
In the invention, the BCSLTM-SA composite microwave dielectric ceramic consists of BCSLTM and SA (SmAlO)3) The BCSLTM has a positive resonant frequency temperature coefficient, and the SA has a negative resonant frequency temperature coefficient; the BCSLTM-SA composite microwave dielectric ceramic comprises BCSLTM and SmAlO3The two crystal phase structures not only lead the resonance frequency temperature coefficient of the microwave dielectric ceramic after being compounded to approach zero, but also improve the Q multiplied by f value of the ceramic; meanwhile, a small amount of Mn replaces Ti and is mainly used as an acceptor for doping, on one hand, the radius of Mn atoms is slightly larger than that of Ti, the addition of Mn can stabilize the space structure and improve the Qxf value, and on the other hand, the valence change of Mn is utilized in the sintering process to inhibit the reduction of Ti and further improve the Qxf value. The BCSLTM-SA composite microwave dielectric ceramic provided by the invention has a stable structure, a specific dielectric constant and a high Q multiplied by f value, and the temperature coefficient of the resonant frequency is continuously adjustable.
In the present invention, the BCSLTM is in the form of BaCO3、CaCO3、Sm2O3、La2O3、TiO2And MnO2Is compounded by basic raw materials; the SmAlO3With Sm2O3And Al2O3Is compounded with basic material.
In the present invention, the SmAlO3The content of the BCSLTM is 5-15% by mass, namely the corresponding content of the BCSLTM is 85-95% by mass. In the present invention, SmAlO3The addition of (A) is mainly to improve Q multiplied by f value and adjust temperature coefficient of resonance frequency to approach zero; if SmAlO3Is less than 5%, has a low Qxf value, and is SmAlO3When the amount of (2) is more than 15%, the value of Qxf is drastically reduced.
In the present invention, the BCSLTM-SA composite microwave dielectric ceramic preferably further includes:
and (3) an additive.
In the invention, the additive is preferably prepared from the following components in a mass ratio of (40-55): (25-35): (15-30): (2-10): (1-10) SiO2、B2O3、Al2O3ZnO and MgO, more preferably 45: 28: 20: 5: SiO of 22、B2O3、Al2O3ZnO and MgO.
In the present invention, the preparation method of the additive is preferably specifically:
mixing SiO2、B2O3、Al2O3Mixing ZnO and MgO, ball-milling, melting at 1200-1300 ℃ for 10-30 min, separating, crushing and sieving to obtain the additive;
more preferably:
mixing SiO2、B2O3、Al2O3And ZnO and MgO are mixed and ball-milled, then melted for 20min at 1250 ℃, and then crushed and sieved after separation to obtain the additive.
The ball milling equipment is not particularly limited in the present invention, and a ball mill known to those skilled in the art may be used. In the present invention, the time for the ball milling is preferably 20 to 24 hours, and more preferably 24 hours. In the present invention, the separation is preferably performed by extraction with water, and the present invention is not particularly limited thereto. The process of the present invention is not particularly limited, and the crushing method known to those skilled in the art may be used. In the present invention, the size of the mesh of the screen is preferably 150 to 250 mesh, and more preferably 200 mesh. By adopting the preparation method, the refined additive can be obtained, and the subsequent use is convenient.
In the invention, the amount of the additive is preferably 0.1-2% of the mass of the BCSLTM-SA composite microwave dielectric ceramic, and more preferably 0.5% of the mass of the pre-sintering material.
In the invention, the additive can reduce the sintering temperature, inhibit titanium reduction and improve the Q multiplied by f value.
The invention also provides a preparation method of the BCSLTM-SA composite microwave dielectric ceramic, which comprises the following steps:
a) mixing BaCO3、CaCO3、Sm2O3、La2O3、TiO2And MnO2After mixing, carrying out primary grinding treatment, and then carrying out primary presintering to obtain a BCSLTM presintering material; simultaneously, Sm is added2O3And Al2O3After mixing, carrying out secondary grinding treatment, and then carrying out secondary pre-sintering to obtain an SA pre-sintering material;
b) mixing the BCSLTM pre-sintering material and the SA pre-sintering material obtained in the step a), and then grinding for the third time to obtain powder; adding an adhesive into the powder for granulation molding to obtain a ceramic green body; and finally, sintering the obtained ceramic green body to obtain the BCSLTM-SA composite microwave dielectric ceramic.
Firstly, BaCO is mixed with the mixture3、CaCO3、Sm2O3、La2O3、TiO2And MnO2After mixing, carrying out primary grinding treatment, and then carrying out primary presintering to obtain the BCSLTM presintering material. The invention is to the BaCO3、CaCO3、Sm2O3、La2O3、TiO2And MnO2The source of (A) is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the first grinding process preferably includes:
mixing the mixed raw materials, zirconium balls and water in a ratio of 1: (1.5-2.5): (1.5-2.5), ball-milling for 6-10 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain a mixed material after primary grinding treatment;
more preferably:
mixing the mixed raw materials, zirconium balls and water in a ratio of 1: 2: 2, ball-milling for 6 hours at the rotating speed of 250r/min, and then drying at 150 ℃ to obtain a mixed material after the first grinding treatment.
The ball milling equipment is not particularly limited in the present invention, and a planetary ball mill well known to those skilled in the art may be used.
After the mixed material after the first grinding treatment is obtained, the mixed material obtained after the first grinding treatment is subjected to first presintering to obtain a BCSLTM presintering material. In the invention, the temperature of the first presintering is preferably 800-1100 ℃, and more preferably 850 ℃; the heating rate of the first pre-sintering is preferably 2.5-3.5 ℃/min, and more preferably 3 ℃/min; the heat preservation time of the first pre-sintering is preferably 2h to 3h, and more preferably 3 h.
After the first presintering is finished, the method preferably further comprises the step of cooling the obtained BCSLTM presintering material; the furnace cooling solution known to those skilled in the art may be used, and the present invention is not limited thereto.
Meanwhile, the invention mixes Sm2O3And Al2O3And after mixing, performing secondary grinding treatment, and performing secondary pre-sintering to obtain the SA pre-sintering material. In the invention, the Al is2O3The source of (A) is not particularly limited, and commercially available products known to those skilled in the art may be used. In the present invention, the Sm is2O3And Al2O3In an amount according to SmAlO3The stoichiometric ratio of (c) was calculated.
In the present invention, the second grinding treatment preferably includes:
mixing the mixed raw materials, zirconium balls and water in a ratio of 1: (1.5-2.5): (1.5-2.5), ball-milling for 6-10 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain a mixed material after the second grinding treatment;
more preferably:
mixing the mixed raw materials, zirconium balls and water in a ratio of 1: 2: 2, ball-milling for 6 hours at the rotating speed of 250r/min, and then drying at 150 ℃ to obtain a mixed material after the second grinding treatment.
The ball milling equipment is not particularly limited in the present invention, and a planetary ball mill well known to those skilled in the art may be used.
After the mixed material after the second grinding treatment is obtained, the obtained mixed material after the second grinding treatment is subjected to second pre-sintering to obtain the SA pre-sintering material. In the invention, the temperature of the second pre-sintering is preferably 800-1100 ℃, and more preferably 1100 ℃; the heating rate of the second pre-sintering is preferably 2.5-3.5 ℃/min, and more preferably 3 ℃/min; the heat preservation time of the second pre-sintering is preferably 2h to 3h, and more preferably 2 h.
After the second pre-sintering is completed, the method preferably further comprises the step of cooling the obtained SA pre-sintering material; the furnace cooling solution known to those skilled in the art may be used, and the present invention is not limited thereto.
After the BCSLTM pre-sintering material and the SA pre-sintering material are respectively obtained, the obtained BCSLTM pre-sintering material and the SA pre-sintering material are mixed and ground for the third time to obtain powder; adding an adhesive into the powder for granulation molding to obtain a ceramic green body; and finally, sintering the obtained ceramic green body to obtain the BCSLTM-SA composite microwave dielectric ceramic.
In the present invention, before the third polishing treatment, it is preferable to further include:
and mixing the obtained BCSLTM pre-sintered material and SA pre-sintered material with additives, and then grinding for the third time to obtain powder. In the present invention, the additive is the same as that described in the above technical solution, and is not described herein again. In the present invention, the amount of the additive is preferably 0.1% to 2%, more preferably 0.5% of the total mass of the BCSLTM pre-sinter and the SA pre-sinter.
In the present invention, the third grinding treatment preferably includes:
mixing the mixed raw materials, zirconium balls and water in a ratio of 1: (1.5-2.5): (1.5-2.5), ball-milling for 6-10 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain powder;
more preferably:
mixing the mixed raw materials, zirconium balls and water in a ratio of 1: 2: 2, ball milling for 10 hours at the rotating speed of 250r/min, and then drying at the temperature of 80 ℃ to obtain powder.
The ball milling equipment is not particularly limited in the present invention, and a planetary ball mill well known to those skilled in the art may be used.
After the powder is obtained, adding an adhesive into the powder for granulation molding to obtain a ceramic green body; and finally, sintering the obtained ceramic green body to obtain the BCSLTM-SA composite microwave dielectric ceramic. In the present invention, theThe adhesive has enough viscosity, can ensure good formability and mechanical strength of the blank, and can be completely volatilized after high-temperature calcination, so that residual impurities of the adhesive are not left in the blank. In the present invention, the binder is preferably a polyvinyl alcohol aqueous solution with a mass percentage of 6% to 8%, and more preferably a polyvinyl alcohol aqueous solution with a mass percentage of 7%. In the present invention, the polyvinyl alcohol is converted into CO after high-temperature calcination (subsequent sintering process)2And H2O, can be completely volatilized.
In the invention, the mass ratio of the powder to the adhesive is 100: (7-10), more preferably 100: 7.
in the present invention, the granulation molding process preferably includes:
adding an adhesive into the powder, granulating and grinding for 0.5-1.5 h, sieving with a 70-90-mesh sieve, and pressing and molding the obtained powder under the pressure of 80-120 MPa to obtain a ceramic green body;
more preferably:
and adding an adhesive into the powder, granulating and grinding for 1h, sieving by using an 80-mesh sieve, and pressing and molding the obtained powder under the pressure of 100MPa to obtain a ceramic green body. In the invention, the granulating and grinding process can uniformly mix the powder and the adhesive and granulate.
In the present invention, the ceramic green body is preferably a thin cylindrical green body having a thickness of 4mm to 10mm and a diameter of 8mm to 20mm, and more preferably a thin cylindrical green body having a thickness of 6mm and a diameter of 13mm (a cylinder having a diameter to height ratio of about 2.0).
In the invention, the sintering temperature is preferably 1000-1100 ℃, and more preferably 1050 ℃; the heating rate of the sintering is preferably 2.5-3.5 ℃/min, more preferably 3 ℃/min; the heat preservation time for sintering is preferably 2h to 4h, and more preferably 2 h.
After sintering, the invention preferably also comprises the step of cooling the sintered product to obtain BCSLTM-SA composite microwave dielectric ceramic; the furnace cooling solution known to those skilled in the art may be used, and the present invention is not limited thereto.
The preparation method provided by the invention is simple, the sintering temperature is low, only 1000-1100 ℃ is needed, and the cost is low; and the method meets the requirement of environmental protection, has no toxicity and no pollution to the environment, is suitable for large-scale industrialization, and has very wide development prospect.
The invention provides BCSLTM-SA composite microwave dielectric ceramic and a preparation method thereof, wherein the BCSLTM-SA composite microwave dielectric ceramic comprises the following components: BCSLTM and SmAlO3(ii) a Wherein the SmAlO is3The mass percentage of the component (A) is 5-15%. Compared with the prior art, the BCSLTM-SA composite microwave dielectric ceramic provided by the invention consists of BCSLTM and SA (SmAlO) in a specific ratio3) Wherein BCSLTM is compounded with BaCO3、CaCO3、Sm2O3、La2O3、TiO2And MnO2Is compounded with Sm as basic material and Sm as SA2O3And Al2O3Is compounded by basic raw materials; the BCSLTM-SA composite microwave dielectric ceramic comprises BCSLTM and SmAlO3The two crystal phase structures not only lead the resonance frequency temperature coefficient of the microwave dielectric ceramic after being compounded to approach zero, but also improve the Q multiplied by f value of the ceramic; meanwhile, a small amount of Mn replaces Ti and is mainly used as an acceptor for doping, on one hand, the radius of Mn atoms is slightly larger than that of Ti, the addition of Mn can stabilize the space structure and improve the Qxf value, and on the other hand, the valence change of Mn is utilized in the sintering process to inhibit the reduction of Ti and further improve the Qxf value. The BCSLTM-SA composite microwave dielectric ceramic provided by the invention has a stable structure, a specific dielectric constant and a high Q multiplied by f value, and the temperature coefficient of the resonant frequency is continuously adjustable. Experimental results show that the dielectric constant of the BCSLTM-SA composite microwave dielectric ceramic is 56-68, the Qxf value is 20432 GHz-29279 GHz, and compared with other systems of microwave dielectric ceramics with the same dielectric constant, the system has the advantages of large Qxf value and low dielectric loss; meanwhile, the temperature coefficient of the resonance frequency is continuously adjustable between-5 ppm/DEG C and +5 ppm/DEG C, and the formula can be flexibly adjusted.
In addition, the preparation method provided by the invention is simple, the sintering temperature is low, only 1000-1100 ℃, and the cost is low; and the method meets the requirement of environmental protection, has no toxicity and no pollution to the environment, is suitable for large-scale industrialization, and has very wide development prospect.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials of the medicines used in the following examples of the present invention are all commercially available products; wherein the adhesive is 7% polyvinyl alcohol aqueous solution by mass percent; the additive is a composite oxide and is prepared from the following components in a mass ratio of 45: 28: 20: 5: SiO of 22、B2O3、Al2O3ZnO and MgO, and the preparation method specifically comprises the following steps:
mixing SiO2、B2O3、Al2O3And ZnO and MgO are mixed and ball-milled for 24 hours, dried and sieved, then melted for 20 minutes at 1250 ℃, then extracted and separated by deionized water, and sieved by a 200-mesh sieve after being crushed to obtain the additive.
Example 1
(1) 34.3517g of BaCO were weighed out3、5.808g CaCO3、75.8999g Sm2O3、29.7767gLa2O3、104.1638g TiO2And 0.6411g MnO2Mixing to obtain a first mixture; mixing the first mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball milling for 6 hours by using a planetary mill wet method, drying at 150 ℃, pre-burning for 3 hours at 850 ℃ (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and cooling along with a furnace to obtain the BCSLTM pre-burning material.
(2) According to SmAlO3193.4339g of Sm were weighed out in a molar ratio of2O3And 56.5661g Al2O3Mixing to obtain a second mixture; mixing the second mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball-milling for 6h by using a planetary mill wet method, drying at 150 ℃, pre-sintering for 2h at 1100 ℃ (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and cooling along with a furnace to obtain the SA pre-sintering material.
(3) Weighing 95g of BCSLTM pre-sintered material, 5g of SA pre-sintered material and 0.5g of additive, and mixing to obtain a third mixture; mixing the third mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball-milling for 10 hours by using a planetary wet method, and drying at 80 ℃ to obtain BCSLTM-SA powder; adding a bonding agent accounting for 7% of the powder mass into the BCSLTM-SA powder, granulating and grinding for 1h, sieving by a 40-mesh sieve, pressing the powder (the pressure is 100MPa) into a thin cylindrical blank body with the thickness of 6mm and the diameter of 13mm, sintering the blank body at 1050 ℃ to form ceramic, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and cooling along with a furnace to obtain the BCSLTM-SA composite microwave dielectric ceramic; the BCSLTM-SA composite microwave dielectric ceramic comprises BCSLTM and SA, wherein the mass of the SA accounts for 5% of the total mass of the BCSLTM-SA composite microwave dielectric ceramic.
The BCSLTM-SA composite microwave dielectric ceramic provided by the embodiment 1 of the invention is tested for various properties, and specifically comprises the following steps:
polishing the surface of the prepared ceramic sample by a metallographic and flannelette medium, and measuring the dielectric constant epsilon by adopting an Agilent 5061B network analyzer according to a Hakki-Coleman methodrAnd tan delta, and calculating to obtain a quality factor Qxf value; in addition, the measurement of the temperature coefficient of the resonant frequency is to directly connect a network analyzer with a constant temperature box, test the change value of the resonant frequency in the temperature range of 20-85 ℃, and then calculate tau according to the formula shown in the formula (I)fA value;
the test results of various performances of the BCSLTM-SA composite microwave dielectric ceramic provided by the embodiment 1 of the invention are as follows:
εr＝67.9，Q×f＝20432GHz，τf＝3.9ppm/℃。
example 2
(1) 34.3517g of BaCO were weighed out3、5.808g CaCO3、75.8999g Sm2O3、29.7767gLa2O3、104.1638g TiO2And 0.6411g MnO2Mixing to obtain a first mixture; mixing the first mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball milling for 6 hours by using a planetary mill wet method, drying at 150 ℃, pre-burning for 3 hours at 850 ℃ (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and cooling along with a furnace to obtain the BCSLTM pre-burning material.
(2) Push buttonAs SmAlO3193.4339g of Sm were weighed out in a molar ratio of2O3And 56.5661g Al2O3Mixing to obtain a second mixture; mixing the second mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball-milling for 6h by using a planetary mill wet method, drying at 150 ℃, pre-sintering for 2h at 1100 ℃ (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and cooling along with a furnace to obtain the SA pre-sintering material.
(3) Weighing 92.5g of BCSLTM pre-sintered material, 7.5g of SA pre-sintered material and 0.5g of additive, and mixing to obtain a third mixture; mixing the third mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball-milling for 10 hours by using a planetary wet method, and drying at 80 ℃ to obtain BCSLTM-SA powder; adding a bonding agent accounting for 7% of the powder mass into the BCSLTM-SA powder, granulating and grinding for 1h, sieving by a 40-mesh sieve, pressing the powder (the pressure is 100MPa) into a thin cylindrical blank body with the thickness of 6mm and the diameter of 13mm, sintering the blank body at 1050 ℃ to form ceramic, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and cooling along with a furnace to obtain the BCSLTM-SA composite microwave dielectric ceramic; the BCSLTM-SA composite microwave dielectric ceramic comprises BCSLTM and SA, wherein the mass of the SA accounts for 7.5% of the total mass of the BCSLTM-SA composite microwave dielectric ceramic.
The BCSLTM-SA composite microwave dielectric ceramic provided by the embodiment 2 of the invention is tested according to the test method provided by the embodiment 1, and the test result is as follows:
εr＝65.35，Q×f＝22651GHz，τf＝1.85ppm/℃。
example 3
(1) 34.3517g of BaCO were weighed out3、5.808g CaCO3、75.8999g Sm2O3、29.7767g La2O3、104.1638g TiO2And 0.6411g MnO2Mixing to obtain a first mixture; mixing the first mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball milling for 6 hours by using a planetary mill wet method, drying at 150 ℃, pre-burning for 3 hours at 850 ℃ (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and cooling along with a furnace to obtain the BCSLTM pre-burning material.
(2) According to SmAlO3Weighing 193 mol ratio.4339g Sm2O3And 56.5661g Al2O3Mixing to obtain a second mixture; mixing the second mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball-milling for 6h by using a planetary mill wet method, drying at 150 ℃, pre-sintering for 2h at 1100 ℃ (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and cooling along with a furnace to obtain the SA pre-sintering material.
(3) Weighing 90g of BCSLTM pre-sintered material, 10g of SA pre-sintered material and 0.5g of additive, and mixing to obtain a third mixture; mixing the third mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball-milling for 10 hours by using a planetary wet method, and drying at 80 ℃ to obtain BCSLTM-SA powder; adding a bonding agent accounting for 7% of the powder mass into the BCSLTM-SA powder, granulating and grinding for 1h, sieving by a 40-mesh sieve, pressing the powder (the pressure is 100MPa) into a thin cylindrical blank body with the thickness of 6mm and the diameter of 13mm, sintering the blank body at 1050 ℃ to form ceramic, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and cooling along with a furnace to obtain the BCSLTM-SA composite microwave dielectric ceramic; the BCSLTM-SA composite microwave dielectric ceramic comprises BCSLTM and SA, wherein the mass of the SA accounts for 10% of the total mass of the BCSLTM-SA composite microwave dielectric ceramic.
The BCSLTM-SA composite microwave dielectric ceramic provided by the embodiment 3 of the invention is tested according to the test method provided by the embodiment 1, and the test result is as follows:
εr＝62.8，Q×f＝24886GHz，τf＝-0.2ppm/℃。
example 4
(1) 34.3517g of BaCO were weighed out3、5.808g CaCO3、75.8999g Sm2O3、29.7767gLa2O3、104.1638g TiO2And 0.6411g MnO2Mixing to obtain a first mixture; mixing the first mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball milling for 6 hours by using a planetary mill wet method, drying at 150 ℃, pre-burning for 3 hours at 850 ℃ (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and cooling along with a furnace to obtain the BCSLTM pre-burning material.
(2) According to SmAlO3193.4339g of Sm were weighed out in a molar ratio of2O3And 56.5661g Al2O3Mixing to obtain a second mixture; mixing the second mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball-milling for 6h by using a planetary mill wet method, drying at 150 ℃, pre-sintering for 2h at 1100 ℃ (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and cooling along with a furnace to obtain the SA pre-sintering material.
(3) Weighing 87.5g of BCSLTM pre-sintered material, 12.5g of SA pre-sintered material and 0.5g of additive, and mixing to obtain a third mixture; mixing the third mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball-milling for 10 hours by using a planetary wet method, and drying at 80 ℃ to obtain BCSLTM-SA powder; adding a bonding agent accounting for 7% of the powder mass into the BCSLTM-SA powder, granulating and grinding for 1h, sieving by a 40-mesh sieve, pressing the powder (the pressure is 100MPa) into a thin cylindrical blank body with the thickness of 6mm and the diameter of 13mm, sintering the blank body at 1050 ℃ to form ceramic, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and cooling along with a furnace to obtain the BCSLTM-SA composite microwave dielectric ceramic; the BCSLTM-SA composite microwave dielectric ceramic comprises BCSLTM and SA, wherein the mass of the SA accounts for 12.5% of the total mass of the BCSLTM-SA composite microwave dielectric ceramic.
The BCSLTM-SA composite microwave dielectric ceramic provided by the embodiment 4 of the invention is tested according to the test method provided by the embodiment 1, and the test result is as follows:
εr＝60.25，Q×f＝27497GHz，τf＝-2.25ppm/℃。
example 5
(1) 34.3517g of BaCO were weighed out3、5.808g CaCO3、75.8999g Sm2O3、29.7767gLa2O3、104.1638g TiO2And 0.6411g MnO2Mixing to obtain a first mixture; mixing the first mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball milling for 6 hours by using a planetary mill wet method, drying at 150 ℃, pre-burning for 3 hours at 850 ℃ (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and cooling along with a furnace to obtain the BCSLTM pre-burning material.
(2) According to SmAlO3193.4339g of Sm were weighed out in a molar ratio of2O3And 56.5661g Al2O3Are mixed to obtainA second mixed material; mixing the second mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball-milling for 6h by using a planetary mill wet method, drying at 150 ℃, pre-sintering for 2h at 1100 ℃ (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and cooling along with a furnace to obtain the SA pre-sintering material.
(3) Weighing 85g of BCSLTM pre-sintered material, 15g of SA pre-sintered material and 0.5g of additive, and mixing to obtain a third mixture; mixing the third mixture, zirconium balls and deionized water in a ratio of 1: 2: 2, ball-milling for 10 hours by using a planetary wet method, and drying at 80 ℃ to obtain BCSLTM-SA powder; adding a bonding agent accounting for 7% of the powder mass into the BCSLTM-SA powder, granulating and grinding for 1h, sieving by a 40-mesh sieve, pressing the powder (the pressure is 100MPa) into a thin cylindrical blank body with the thickness of 6mm and the diameter of 13mm, sintering the blank body at 1050 ℃ to form ceramic, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and cooling along with a furnace to obtain the BCSLTM-SA composite microwave dielectric ceramic; the BCSLTM-SA composite microwave dielectric ceramic comprises BCSLTM and SA, wherein the mass of the SA accounts for 15% of the total mass of the BCSLTM-SA composite microwave dielectric ceramic.
The BCSLTM-SA composite microwave dielectric ceramic provided by the embodiment 5 of the invention is tested according to the test method provided by the embodiment 1, and the test result is as follows:
εr＝57.7，Q×f＝29279GHz，τf＝-4.3ppm/℃。
in summary, the dielectric constant of the BCSLTM-SA composite microwave dielectric ceramic provided by the invention is 56-68, the Qxf value is 20432 GHz-29279 GHz, and compared with other systems of microwave dielectric ceramics with the same dielectric constant, the system has large Qxf value and low dielectric loss; meanwhile, the temperature coefficient of the resonance frequency is continuously adjustable between-5 ppm/DEG C and +5 ppm/DEG C, and the formula can be flexibly adjusted.
In addition, the preparation method provided by the invention is simple, the sintering temperature is low, only 1000-1100 ℃, and the cost is low; and the method meets the requirement of environmental protection, has no toxicity and no pollution to the environment, is suitable for large-scale industrialization, and has very wide development prospect.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A preparation method of BCSLTM-SA composite microwave dielectric ceramic comprises the following steps:
a) 34.3517g of BaCO3、5.808g CaCO3、75.8999g Sm2O3、29.7767g La2O3、104.1638g TiO2And 0.6411g MnO2After mixing, carrying out primary grinding treatment, and then carrying out primary presintering to obtain a BCSLTM presintering material; simultaneously, Sm is added2O3And Al2O3After mixing, carrying out secondary grinding treatment, and then carrying out secondary pre-sintering to obtain an SA pre-sintering material;
b) mixing the BCSLTM pre-sintered material and the SA pre-sintered material obtained in the step a) with an additive, and then carrying out third grinding treatment to obtain powder; adding an adhesive into the powder for granulation molding to obtain a ceramic green body; finally, sintering the obtained ceramic green body to obtain BCSLTM-SA composite microwave dielectric ceramic; the BCSLTM-SA composite microwave dielectric ceramic consists of BCSLTM and SmAlO3Is prepared by compounding SmAlO3The mass percentage content of the compound is 5 to 15 percent;
the additive is prepared from the following components in percentage by mass (40-55): (25-35): (15-30): (2-10): (1-10) SiO2、B2O3、Al2O3ZnO and MgO;
the preparation method of the additive specifically comprises the following steps:
mixing SiO2、B2O3、Al2O3Mixing ZnO and MgO, ball-milling, melting at 1200-1300 ℃ for 10-30 min, separating, crushing and sieving to obtain the additive;
the amount of the additive is 0.1-2% of the mass of the BCSLTM-SA composite microwave dielectric ceramic.
2. The preparation method according to claim 1, wherein the first grinding treatment in step a) is specifically performed by:
mixing the mixed raw materials, zirconium balls and water in a ratio of 1: (1.5-2.5): (1.5-2.5), ball-milling for 6-10 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain the mixed material after the first grinding treatment.
3. The preparation method of claim 1, wherein the temperature of the first presintering in the step a) is 800-1100 ℃, the heating rate is 2.5-3.5 ℃/min, and the holding time is 2-3 h.
4. The preparation method according to claim 1, wherein the adhesive in the step b) is a polyvinyl alcohol aqueous solution with the mass percentage of 6-8%;
the mass ratio of the powder to the adhesive is 100: (7-10).
5. The preparation method according to claim 1, wherein the granulating and forming process in the step b) is specifically as follows:
adding an adhesive into the powder, granulating and grinding for 0.5-1.5 h, sieving with a 70-90 mesh sieve, and pressing and molding the obtained powder under the pressure of 80-120 MPa to obtain the ceramic green body.
6. The preparation method according to claim 1, wherein the sintering temperature in step b) is 1000 ℃ to 1100 ℃, the heating rate is 2.5 ℃/min to 3.5 ℃/min, and the holding time is 2h to 4 h.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090116587A (en) * | 2008-05-06 | 2009-11-11 | 한국과학기술연구원 | Composite dielectric thin film, capacitor and field effect transistor using the same, and each fabrication method thereof |
| CN102757219A (en) * | 2012-07-31 | 2012-10-31 | 嘉兴佳利电子股份有限公司 | Two-phase compound microwave medium ceramic material and preparation method thereof |
| CN103601487A (en) * | 2013-11-29 | 2014-02-26 | 电子科技大学 | (SrCa)TiO3-LaAlO3-based microwave dielectric ceramic material and preparation method thereof |
| CN104844194A (en) * | 2015-04-13 | 2015-08-19 | 电子科技大学 | A-B site simultaneously substituting microwave dielectric ceramic material and preparation method thereof |
| CN105601271A (en) * | 2016-01-13 | 2016-05-25 | 南京攀思特电子科技有限公司 | Middle-permittivity microwave dielectric ceramic and manufacturing method thereof |
| CN105837213A (en) * | 2016-03-29 | 2016-08-10 | 电子科技大学 | Microwave dielectric ceramic material doped with ReAlO3 and preparation method thereof. |
| CN106032318A (en) * | 2015-03-12 | 2016-10-19 | 中国科学院上海硅酸盐研究所 | A low-temperature co-fired ceramic material and a preparing method thereof |
| CN108264348A (en) * | 2018-01-30 | 2018-07-10 | 华中科技大学 | A kind of high dielectric constant low loss microwave dielectric ceramics and preparation method thereof |
| CN108863362A (en) * | 2018-08-02 | 2018-11-23 | 广东国华新材料科技股份有限公司 | A kind of nanometer microwave medium ceramic material and preparation method thereof |
| CN108863347A (en) * | 2018-08-02 | 2018-11-23 | 广东国华新材料科技股份有限公司 | A kind of microwave-medium ceramics and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011075123A1 (en) * | 2009-12-16 | 2011-06-23 | Skyworks Solutions, Inc. | Dielectric ceramic materials and associated methods |
-
2019
- 2019-03-12 CN CN201910184979.5A patent/CN109761603B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090116587A (en) * | 2008-05-06 | 2009-11-11 | 한국과학기술연구원 | Composite dielectric thin film, capacitor and field effect transistor using the same, and each fabrication method thereof |
| CN102757219A (en) * | 2012-07-31 | 2012-10-31 | 嘉兴佳利电子股份有限公司 | Two-phase compound microwave medium ceramic material and preparation method thereof |
| CN103601487A (en) * | 2013-11-29 | 2014-02-26 | 电子科技大学 | (SrCa)TiO3-LaAlO3-based microwave dielectric ceramic material and preparation method thereof |
| CN106032318A (en) * | 2015-03-12 | 2016-10-19 | 中国科学院上海硅酸盐研究所 | A low-temperature co-fired ceramic material and a preparing method thereof |
| CN104844194A (en) * | 2015-04-13 | 2015-08-19 | 电子科技大学 | A-B site simultaneously substituting microwave dielectric ceramic material and preparation method thereof |
| CN105601271A (en) * | 2016-01-13 | 2016-05-25 | 南京攀思特电子科技有限公司 | Middle-permittivity microwave dielectric ceramic and manufacturing method thereof |
| CN105837213A (en) * | 2016-03-29 | 2016-08-10 | 电子科技大学 | Microwave dielectric ceramic material doped with ReAlO3 and preparation method thereof. |
| CN108264348A (en) * | 2018-01-30 | 2018-07-10 | 华中科技大学 | A kind of high dielectric constant low loss microwave dielectric ceramics and preparation method thereof |
| CN108863362A (en) * | 2018-08-02 | 2018-11-23 | 广东国华新材料科技股份有限公司 | A kind of nanometer microwave medium ceramic material and preparation method thereof |
| CN108863347A (en) * | 2018-08-02 | 2018-11-23 | 广东国华新材料科技股份有限公司 | A kind of microwave-medium ceramics and preparation method thereof |
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