Li3Mg2SbO6-based microwave dielectric ceramic material easy to sinter and with high q value, and preparation method therefor

Abstract

A Li.sub.3Mg.sub.2SbO.sub.6-based microwave dielectric ceramic material easy to sinter and with high Q value, and a preparation method thereof are disclosed. A chemical formula of the material is Li.sub.3(Mg.sub.1-xZn.sub.x).sub.2SbO.sub.6, wherein 0.02≤x≤0.08. The preparation method includes: 1) mixing and ball-milling Sb.sub.2O.sub.3 and Li.sub.2CO.sub.3 according to a chemical ratio and then drying, and conducting pre-sintering to obtain a Li.sub.3SbO.sub.4 phase; and 2) mixing and ball-milling MgO, ZnO and Li.sub.3SbO.sub.4 powder according a chemical ratio of Li.sub.3(Mg.sub.1-xZn.sub.x).sub.2SbO.sub.6 and then drying, conducting granulation and sieving after adding an adhesive, pressing into a cylindrical body, and sintering the cylindrical body into ceramic in the air at 1325° C. and under normal pressure, wherein a dielectric constant is 7.2-8.5, a quality factor is 51844-97719 GHz, and a temperature coefficient of resonance frequency is −14-1 ppm/° C.

Claims

1. A preparation method for a Li.sub.3Mg.sub.2SbO.sub.6-based microwave dielectric ceramic material, comprising the following steps: (1.1) preparing Li.sub.3SbO.sub.4 powder from Li.sub.2CO.sub.3 and Sb.sub.2O.sub.3 with a purity of 99% according to a chemical ratio of Li.sub.3SbO.sub.4; (1.2) mixing the Li.sub.3SbO.sub.4 powder uniformly, and mixing the Li.sub.3SbO.sub.4 powder by a wet milling method for 8 hours with pure water as a dispersing agent and a zirconium oxide ball (with a diameter of 3-15 mm) as a ball-milling medium to obtain a first milled product, wherein a weight ratio of the Li.sub.3SbO.sub.4 powder to the pure water to the zirconium oxide ball is 1:2:1.5; drying the first milled product at 120° C. after discharging; after passing the first milled product through a 80-mesh sieve, heating the first milled product from room temperature to 900° C. at a heating rate of 2° C./min, and conducting a heat preservation for 4 hours to prepare a Li.sub.3SbO.sub.4 microwave dielectric phase; (2.1) preparing a powder mixture from MgO, ZnO, and the Li.sub.3SbO.sub.4 microwave dielectric phase according to a chemical ratio of a molecular formula of Li.sub.3(Mg.sub.1-xZn.sub.x).sub.2SbO.sub.6 (0.02≤x≤0.08), the MgO and the ZnO each has a purity of 99%; (2.2) uniformly mixing the powder mixture prepared in step (2.1), mixing the powder mixture by the wet milling method for 8 hours with the pure water as the dispersing agent and the zirconium oxide ball (with a diameter of 3-15 mm) as the ball-milling medium to obtain a second milled product, wherein a weight ratio of the powder mixture to the pure water to the zirconium oxide ball is 1:2:1.5; drying the second milled product at 120° C. after discharging, passing the second milled product through a 80-mesh sieve, and adding an organic adhesive to the second milled product at a weight ratio of 6-10 wt % to obtain a third mixture; conducting a granulation to the third mixture to obtain a granulated mixture; after passing the granulated mixture through a 120-mesh sieve, pressing the granulated mixture into a cylindrical green body with a diameter of 10-12 mm and a height of 5-6 mm, and putting the cylindrical green body into a muffle furnace for sintering in air at 1325° C. for 5 hours to prepare a sintered Li.sub.3(Mg.sub.1-xZn.sub.x).sub.2SbO.sub.6 microwave dielectric ceramic; and (2.3) polishing two surfaces of the sintered Li.sub.3(Mg.sub.1-xZn.sub.x).sub.2SbO.sub.6 microwave dielectric ceramic to prepare a finished product to be tested.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an XRD spectrum of a ceramic material prepared by sintering at 1325° C. according to embodiments 1 to 4 of the present invention;

(2) FIGS. 2A-2D show surface SEM photos of a ceramic material prepared by sintering at 1325° C. according to Embodiments 1 to 4 of the present invention (FIGS. 2A, 2B, 2C, and 2D correspond to Embodiments 1, 2, 3, and 4 respectively); and

(3) FIG. 3 is a drawing of microwave dielectric properties (including dielectric constant, quality factor and temperature coefficient of resonant frequency) of a ceramic material prepared by sintering at 1325° C. according to Embodiments 1 to 4 of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(4) Implementation of the present invention is described below by specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from contents disclosed in the specification. The present invention can be implemented or applied through other different specific implementations. Various modifications or changes can be made to various details in the specification based on different viewpoints and applications without departing from the spirit of the present invention.

Embodiment 1

(5) The embodiment provides a Li.sub.3Mg.sub.2SbO.sub.6-based microwave dielectric ceramic material easy to sinter and with high Q value. The chemical formula of the ceramic material is Li.sub.3(Mg.sub.0.98Zn.sub.0.02).sub.2SbO.sub.6 (Li.sub.3(Mg.sub.1-xZn.sub.x).sub.2SbO.sub.6, x=0.02).

(6) The preparation method includes the following steps:

(7) (1.1) Li.sub.3SbO.sub.4 powder was prepared from Li.sub.2CO.sub.3 and Sb.sub.2O.sub.3 with a purity of 99% according to a chemical ratio of Li.sub.3SbO.sub.4; and

(8) (1.2) the above powder was mixed uniformly, mixing was conducted by a wet milling method for 8 hours with pure water as a dispersing agent and a zirconium oxide ball (with a diameter of 3-15 mm) as a ball-milling medium according to a weight ratio of raw material to pure water to zirconium oxide ball being 1:2:1.5, drying was conducted at 120° C. after discharging, heating was conducted from room temperature to 900° C. at a heating rate of 2° C./min after the mixture passed through a 80-mesh sieve, and heat preservation was conducted for 4 hours to prepare a Li.sub.3SbO.sub.4 microwave dielectric phase.

(9) (2.1) Powder was prepared from MgO and ZnO with a purity of 99% as well as the Li.sub.3SbO.sub.4 microwave dielectric phase prepared in the above step according to a molecular formula of Li.sub.3(Mg.sub.0.98Zn.sub.0.02).sub.2SbO.sub.6 (0.02≤x≤0.08);

(10) (2.2) the powder prepared in the above step was mixed uniformly, mixing was conducted by a wet milling method for 8 hours with pure water as a dispersing agent and a zirconium oxide ball (with a diameter of 3-15 mm) as a ball-milling medium according to a weight ratio of raw material to pure water to zirconium oxide ball being 1:2:1.5, drying was conducted at 120° C. after discharging, the mixture passed through a 80-mesh sieve, an organic adhesive was added according to a weight ratio of 6-10 wt % to conduct granulation, granules were pressed into a cylindrical green body with a diameter of 10-12 mm and a height of 5-6 mm after the granules passed through a 120-mesh sieve, and the green body was put into a muffle furnace for sintering in the air at 1325° C. for 5 hours to prepare a sintered microwave dielectric ceramic;

(11) (2.3) two surfaces of the sintered Li.sub.3(Mg.sub.0.98Zn.sub.0.02).sub.2SbO.sub.6 ceramic were polished to prepare a finished product to be tested;

(12) (2.4) a measured apparent density of the material was obtained by an Archimedes drainage method;

(13) (2.5) phase structure information of the material was obtained by a Miniflex X ray diffraction instrument; and

(14) (2.6) an apparent morphology of the material was obtained by JEOL JSM-6490 SEM.

(15) The microwave dielectric property test which the embodiment relates to adopts a dielectric resonant cavity method provided by Hakki and Coleman to test the dielectric constant and the microwave dielectric property of the cylinder at the resonant frequency, and the microwave dielectric property is tested by an American Agilent N5230A network analysis instrument.

(16) The result of the microwave dielectric property test of Li.sub.3(Mg.sub.0.98Zn.sub.0.02).sub.2SbO.sub.6 ceramic sintered at 1325° C. is as follows: the resonant frequency is 13.512 GHz, the dielectric constant is 8.5, the quality factor is 82400 GHz, and the temperature coefficient of resonance frequency is −14 ppm/° C. The result is shown in FIG. 3.

Embodiment 2

(17) The embodiment provides a Li.sub.3Mg.sub.2SbO.sub.6-based microwave dielectric ceramic material easy to sinter and with high Q value. The chemical formula of the ceramic material is Li.sub.3(Mg.sub.0.96Zn.sub.0.04).sub.2SbO.sub.6 (Li.sub.3(Mg.sub.1-xZn.sub.x).sub.2SbO.sub.6, x=0.04).

(18) The preparation method includes the following steps:

(19) (1.1) Li.sub.3SbO.sub.4 powder was prepared from Li.sub.2CO.sub.3 and Sb.sub.2O.sub.3 with a purity of 99% according to a chemical ratio of Li.sub.3SbO.sub.4; and

(20) (1.2) the above powder was mixed uniformly, mixing was conducted by a wet milling method for 8 hours with pure water as a dispersing agent and a zirconium oxide ball (with a diameter of 3-15 mm) as a ball-milling medium according to a weight ratio of raw material to pure water to zirconium oxide ball being 1:2:1.5, drying was conducted at 120° C. after discharging, heating was conducted from room temperature to 900° C. at a heating rate of 2° C./min after the mixture passed through a 80-mesh sieve, and heat preservation was conducted for 4 hours to prepare a Li.sub.3SbO.sub.4 microwave dielectric phase.

(21) (2.1) Powder was prepared from MgO and ZnO with a purity of 99% as well as the Li.sub.3SbO.sub.4 microwave dielectric phase prepared in the above step according to a molecular formula of Li.sub.3(Mg.sub.0.96Zn.sub.0.04).sub.2SbO.sub.6;

(22) (2.2) the powder prepared in the above step was mixed uniformly, mixing was conducted by a wet milling method for 8 hours with pure water as a dispersing agent and a zirconium oxide ball (with a diameter of 3-15 mm) as a ball-milling medium according to a weight ratio of raw material to pure water to zirconium oxide ball being 1:2:1.5, drying was conducted at 120° C. after discharging, the mixture passed through a 80-mesh sieve, an organic adhesive was added according to a weight ratio of 6-10 wt % to conduct granulation, granules were pressed into a cylindrical green body with a diameter of 10-12 mm and a height of 5-6 mm after the granules passed through a 120-mesh sieve, and the green body was put into a muffle furnace for sintering in the air at 1325° C. for 5 hours to prepare a sintered microwave dielectric ceramic;

(23) (2.3) two surfaces of the sintered Li.sub.3(Mg.sub.0.96Zn.sub.0.04).sub.2SbO.sub.6 ceramic were polished to prepare a finished product to be tested;

(24) (2.4) a measured apparent density of the material was obtained by an Archimedes drainage method;

(25) (2.5) phase structure information of the material was obtained by a Miniflex X ray diffraction instrument; and

(26) (2.6) an apparent morphology of the material was obtained by JEOL JSM-6490 SEM.

(27) The microwave dielectric property test which the present invention relates to adopts a dielectric resonant cavity method provided by Hakki and Coleman to test the dielectric constant and the microwave dielectric property of the cylinder at the resonant frequency, and the microwave dielectric property is tested by an American Agilent N5230A network analysis instrument.

(28) The result of the microwave dielectric property test of Li.sub.3(Mg.sub.0.96Zn.sub.0.04).sub.2SbO.sub.6 ceramic sintered at 1325° C. is as follows: the resonant frequency is 13.705 GHz, the dielectric constant is 8.2, the quality factor is 97719 GHz, and the temperature coefficient of resonance frequency is −7 ppm/° C. The result is shown in FIG. 3.

Embodiment 3

(29) The embodiment provides a Li.sub.3Mg.sub.2SbO.sub.6-based microwave dielectric ceramic material easy to sinter and with high Q value. The chemical formula of the ceramic material is Li.sub.3(Mg.sub.0.94Zn.sub.0.06).sub.2SbO.sub.6 (Li.sub.3(Mg.sub.1-xZn.sub.x).sub.2SbO.sub.6, x=0.06).

(30) The preparation method includes the following steps:

(31) (1.1) Li.sub.3SbO.sub.4 powder was prepared from Li.sub.2CO.sub.3 and Sb.sub.2O.sub.3 with a purity of 99% according to a chemical ratio of Li.sub.3SbO.sub.4; and

(32) (1.2) the above powder was mixed uniformly, mixing was conducted by a wet milling method for 8 hours with pure water as a dispersing agent and a zirconium oxide ball (with a diameter of 3-15 mm) as a ball-milling medium according to a weight ratio of raw material to pure water to zirconium oxide ball being 1:2:1.5, drying was conducted at 120° C. after discharging, heating was conducted from room temperature to 900° C. at a heating rate of 2° C./min after the mixture passed through a 80-mesh sieve, and heat preservation was conducted for 4 hours to prepare a Li.sub.3SbO.sub.4 microwave dielectric phase.

(33) (2.1) Powder was prepared from MgO and ZnO with a purity of 99% as well as the Li.sub.3SbO.sub.4 microwave dielectric phase prepared in the above step according to a molecular formula of Li.sub.3(Mg.sub.0.98Zn.sub.0.06).sub.2SbO.sub.6;

(34) (2.2) the powder prepared in the above step was mixed uniformly, mixing was conducted by a wet milling method for 8 hours with pure water as a dispersing agent and a zirconium oxide ball (with a diameter of 3-15 mm) as a ball-milling medium according to a weight ratio of raw material to pure water to zirconium oxide ball being 1:2:1.5, drying was conducted at 120° C. after discharging, the mixture passed through a 80-mesh sieve, an organic adhesive PVA was added according to a weight ratio of 6-10 wt % to conduct granulation, granules were pressed into a cylindrical green body with a diameter of 10-12 mm and a height of 5-6 mm after the granules passed through a 120-mesh sieve, and the green body was put into a muffle furnace for sintering in the air at 1325° C. for 5 hours to prepare a sintered microwave dielectric ceramic;

(35) (2.3) two surfaces of the sintered Li.sub.3(Mg.sub.0.94Zn.sub.0.06).sub.2SbO.sub.6 ceramic were polished to prepare a finished product to be tested;

(36) (2.4) a measured apparent density of the material was obtained by an Archimedes drainage method;

(37) (2.5) phase structure information of the material was obtained by a Miniflex X ray diffraction instrument; and

(38) (2.6) an apparent morphology of the material was obtained by JEOL JSM-6490 SEM.

(39) The microwave dielectric property test which the present invention relates to adopts a dielectric resonant cavity method provided by Hakki and Coleman to test the dielectric constant and the microwave dielectric property of the cylinder at the resonant frequency, and the microwave dielectric property is tested by an American Agilent N5230A network analysis instrument.

(40) The result of the microwave dielectric property test of Li.sub.3(Mg.sub.0.94Zn.sub.0.06).sub.2SbO.sub.6 ceramic sintered at 1325° C. is as follows: the resonant frequency is 13.495 GHz, the dielectric constant is 7.7, the quality factor is 53095 GHz, and the temperature coefficient of resonance frequency is −4 ppm/° C. The result is shown in FIG. 3.

Embodiment 4

(41) The embodiment provides a Li.sub.3Mg.sub.2SbO.sub.6-based microwave dielectric ceramic material easy to sinter and with high Q value. The chemical formula of the ceramic material is Li.sub.3(Mg.sub.0.92Zn.sub.0.08).sub.2SbO.sub.6 (Li.sub.3(Mg.sub.1-xZn.sub.x).sub.2SbO.sub.6, x=0.08).

(42) The preparation method includes the following steps:

(43) (1.1) Li.sub.3SbO.sub.4 powder was prepared from Li.sub.2CO.sub.3 and Sb.sub.2O.sub.3 with a purity of 99% according to a chemical ratio of Li.sub.3SbO.sub.4; and

(44) (1.2) the above powder was mixed uniformly, mixing was conducted by a wet milling method for 8 hours with pure water as a dispersing agent and a zirconium oxide ball (with a diameter of 3-15 mm) as a ball-milling medium according to a weight ratio of raw material to pure water to zirconium oxide ball being 1:2:1.5, drying was conducted at 120° C. after discharging, heating was conducted from room temperature to 900° C. at a heating rate of 2° C./min after the mixture passed through a 80-mesh sieve, and heat preservation was conducted for 4 hours to prepare a Li.sub.3SbO.sub.4 microwave dielectric phase.

(45) (2.1) Powder was prepared from MgO and ZnO with a purity of 99% as well as the Li.sub.3SbO.sub.4 microwave dielectric phase prepared in the above step according to a molecular formula of Li.sub.3(Mg.sub.0.92Zn.sub.0.08).sub.2SbO.sub.6;

(46) (2.2) the powder prepared in the above step was mixed uniformly, mixing was conducted by a wet milling method for 8 hours with pure water as a dispersing agent and a zirconium oxide ball (with a diameter of 3-15 mm) as a ball-milling medium according to a weight ratio of raw material to pure water to zirconium oxide ball being 1:2:1.5, drying was conducted at 120° C. after discharging, the mixture passed through a 80-mesh sieve, an organic adhesive PVA was added according to a weight ratio of 6-10 wt % to conduct granulation, granules were pressed into a cylindrical green body with a diameter of 10-12 mm and a height of 5-6 mm after the granules passed through a 120-mesh sieve, and the green body was put into a muffle furnace for sintering in the air at 1325° C. for 5 hours to prepare a sintered microwave dielectric ceramic;

(47) (2.3) two surfaces of the sintered Li.sub.3(Mg.sub.0.92Zn.sub.0.08).sub.2SbO.sub.6 ceramic were polished to prepare a finished product to be tested;

(48) (2.4) a measured apparent density of the material was obtained by an Archimedes drainage method;

(49) (2.5) phase structure information of the material was obtained by a Miniflex X ray diffraction instrument; and

(50) (2.6) an apparent morphology of the material was obtained by JEOL JSM-6490 SEM. The microwave dielectric property test which the present invention relates to adopts a dielectric resonant cavity method provided by Hakki and Coleman to test the dielectric constant and the microwave dielectric property of the cylinder at the resonant frequency, and the microwave dielectric property is tested by an American Agilent N5230A network analysis instrument.

(51) The result of the microwave dielectric property test of Li.sub.3(Mg.sub.0.92Zn.sub.0.08).sub.2SbO.sub.6 ceramic sintered at 1325° C. is as follows: the resonant frequency is 13.850 GHz, the dielectric constant is 7.2, the quality factor is 51844 GHz, and the temperature coefficient of resonance frequency is −1 ppm/° C. The result is shown in FIG. 3.

(52) In the above four specific embodiments, the quality factor of the Li.sub.3(Mg.sub.0.96Zn.sub.0.04).sub.2SbO.sub.6 ceramic prepared in the embodiment 2 is maximum, namely 97719 GHz, indicating that the energy loss during signal transmission is minimum; the dielectric constant is 8.2; and the temperature coefficient of resonant coefficient is −7 ppm/° C. The temperature coefficient of resonant frequency of the Li.sub.3(Mg.sub.0.92Zn.sub.0.08).sub.2SbO.sub.6 ceramic prepared in embodiment 4 is closest to zero and is −1 ppm/° C., indicating that the Li.sub.3(Mg.sub.0.92Zn.sub.0.08).sub.2SbO.sub.6 ceramic has the best temperature stability; the dielectric constant is 7.2; and the quality factor is 51844 GHz. In the prepared four embodiments, the embodiment 2 has the optimal comprehensive property due to high quality factor Q.

(53) The present invention includes, but is not limited to, the above embodiments, and all embodiments meeting the requirements of the present invention belong to the protection scope of the present invention.

(54) In conclusion, the present invention provides a Li.sub.3Mg.sub.2SbO.sub.6-based microwave dielectric ceramic material easy to sinter and with high Q value, and a preparation method therefor. A microwave dielectric ceramic material with high Q value, which has high quality factor, small dielectric constant and excellent temperature stability, is obtained by modifying Li.sub.3Mg.sub.2SbO.sub.6 ceramic through Zn, which provides an effective solution for high-frequency application of 5G communication microwave dielectric components.

(55) The above embodiments are only intended to exemplarily illustrate the principle and effect of the present invention, but not intended to limit the present invention. Any person skilled in the art can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those with ordinary knowledge in the art without departing the spirit and technical ideal disclosed by the present invention should still be covered within the claims of the present invention.