CN110818412A - Titanium-based non-stoichiometric microwave dielectric ceramic material - Google Patents

Titanium-based non-stoichiometric microwave dielectric ceramic material Download PDF

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CN110818412A
CN110818412A CN201910971617.0A CN201910971617A CN110818412A CN 110818412 A CN110818412 A CN 110818412A CN 201910971617 A CN201910971617 A CN 201910971617A CN 110818412 A CN110818412 A CN 110818412A
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stoichiometric
dielectric ceramic
microwave dielectric
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李玲霞
乔坚栗
杜明昆
罗伟嘉
彭伟
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Tianjin University
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    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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Abstract

The invention discloses a titanium-based non-stoichiometric microwave dielectric ceramic material prepared from MgO and TiO2、Nb2O5、ZrO2As a raw material, the target compound has the expression of Mg1+xTi0.9Zr0.1Nb2O8Wherein x is 0.01 to 0.05. Firstly, raw materials are proportioned according to a stoichiometric formula, ball-milled, dried and sieved, then presintered at 1050 ℃, and then granulated after secondary ball-milling, and pressed into green bodies; sintering the green body at 1225-1275 deg.c to prepare the non-stoichiometric Ti-base microwave dielectric ceramic material. Dielectric constant ε of the present inventionr28.86 to 30.35, quality factor Qf 37389 to 66864GHz, and temperature coefficient of resonance frequency τfIs-19.38 to-26.57 multiplied by 10‑6V. C. The preparation process is simple, the medium-temperature sintering is adopted, and the application prospect is wide.

Description

Titanium-based non-stoichiometric microwave dielectric ceramic material
Technical Field
The invention belongs to a ceramic composition characterized by components, in particular to a ceramic composition characterized by Mg1+xTi0.9Zr0.1Nb2O8A microwave dielectric ceramic material with high Q value and a preparation method thereof, which is the medium temperature sintering of a chemical formula.
Background
Microwave technology is one of the great achievements of recent scientific development. Because microwaves have the advantages of short wavelength, high frequency and the like, the microwaves have good frequency selection characteristics and are widely applied to the fields of mobile communication, satellite communication, military radar, Global Positioning System (GPS), Bluetooth technology, wireless local area network and the like. The development of microwave communication technology puts new requirements on the performance (sensitivity, signal-to-noise ratio, coverage, communication capacity, etc.) and size of microwave devices.
In order to meet different application requirements, microwave dielectric ceramic materials are continuously developed, and novel microwave dielectric ceramic materials with excellent various properties are continuously emerged. The application requirements of the microwave dielectric ceramic material comprise three aspects: a suitable dielectric constant, a higher quality factor Qf (better frequency selectivity) and a smaller temperature coefficient of frequency (high temperature stability).
ATiNb of wolframite structure2O8(a ═ Zn, Mg, Co) is a new microwave dielectric ceramic material, which has received much attention because of its moderate dielectric constant, high Qf value. In which the pure phase ZnTiNb2O8The microwave dielectric properties of the material are as follows: qf 42500GHz, ∈r＝34，τf＝-52×10-6V. C. And a material system MgTiNb similar to the structure2O8The Qf value is only 26200GHz, which limits the further development of this system.
Disclosure of Invention
The invention aims to improve MgTiNb2O8The quality factor of the dielectric ceramic material is suitable for the development direction of high frequency and digitalization of electronic information technology. With MgO, TiO2、Nb2O5、ZrO2Preparing a non-stoichiometric Mg with high quality factor by a simple solid phase method1+xTi0.9Zr0.1Nb2O8Microwave dielectric ceramic material.
The invention is realized by the following technical scheme.
A Ti-base non-stoichiometric microwave dielectric ceramic material is prepared from MgO and TiO2、Nb2O5、ZrO2Is used as a raw material for preparing the high-purity,the target composition is expressed as Mg1+xTi0.9Zr0.1Nb2O8Wherein x is 0.01 to 0.05.
The specific implementation steps are as follows:
(1) mixing MgO and TiO2、Nb2O5、ZrO2Respectively according to the stoichiometric formula Mg1+xTi0.9Zr0.1Nb2O8Mixing x is 0.01-0.05, putting the powder into a polyester tank, adding deionized water and zirconium balls, and performing ball milling for 4-8 hours;
(2) putting the ball-milled raw materials in the step (1) into a drying oven, drying at 80-120 ℃ respectively, and then sieving with a 40-mesh sieve;
(3) putting the powder sieved in the step (2) into a medium-temperature furnace, presintering at 1050 ℃, preserving heat for 2-8 hours, and then sieving by a 40-mesh sieve;
(4) putting the calcined powder in the step (3) into a ball milling tank, adding zirconia balls and deionized water, and carrying out ball milling for 9-12 hours;
(5) putting the ball-milled raw materials in the step (4) into a drying oven, drying, adding 5% polyvinyl alcohol aqueous solution as an adhesive, granulating, sieving with a 80-mesh sieve, and pressing into a green body by using a powder tablet press at a pressure of 4-8 MPa;
(6) and (4) sintering the green body obtained in the step (4) at 1225-1275 ℃, and preserving heat for 2-8 hours to prepare the microwave dielectric ceramic with the medium dielectric constant.
And (2) ball milling is carried out in the step (1) by adopting a planetary ball mill, and the rotating speed of the ball mill is 400 r/min.
The diameter of the green body obtained in the step (5) is 10mm, and the thickness of the green body is 5 mm.
The step (6) is sintering in an air atmosphere
The invention prepares a titanium-based non-stoichiometric microwave dielectric ceramic material Mg by a simple solid-phase synthesis method1+xTi0.9Zr0.1Nb2O8. Its dielectric constant εr28.86 to 30.35, quality factor Qf 37389 to 66864GHz, and temperature coefficient of resonance frequency τfIs-19.38 to-26.57 multiplied by 10-6V. C. The preparation method has simple process, and is suitable for various usesThe method has the advantages of mild sintering and wide application prospect.
Detailed Description
Example 1
In the form of TiO with a purity of more than 99%2(analytically pure), MgO (analytically pure), Nb2O5(analytical grade), ZrO2(analytically pure) is used as an initial raw material, and the microwave dielectric material is prepared by a solid phase method. The specific implementation steps are as follows:
(1) adding TiO into the mixture2、MgO、Nb2O5、ZrO2In stoichiometric formula Mg1.05Ti0.9Zr0.1Nb2O8The materials are mixed, and the powder mixture ratio is as follows: 3.594g of TiO2、2.0974gMgO、13.1576gNb2O5、0.6162gZrO2. Putting the powder into a polyester tank, adding 200ml of deionized water and 150g of zirconium balls, and performing ball milling for 6 hours at the rotating speed of 400 revolutions per minute;
(2) putting the ball-milled raw materials in the step (1) into a drying oven, drying at 100 ℃, and then sieving by a 40-mesh sieve;
(3) putting the powder sieved in the step (2) into a medium temperature furnace, presintering at 1050 ℃, preserving heat for 4 hours, and then sieving by a 40-mesh sieve;
(4) putting the calcined powder in the step (3) into a ball milling tank, adding 200ml of deionized water and 150g of zirconia balls, and carrying out ball milling for 12 hours at the rotating speed of 400 r/m;
(5) putting the ball-milled raw materials in the step (4) into a drying oven, drying, adding 5% polyvinyl alcohol aqueous solution as an adhesive, granulating, sieving with a 80-mesh sieve, and pressing into a green body by using a powder tablet press under the pressure of 4 MPa;
(6) sintering the green body obtained in the step (5) at 1250 ℃, and preserving heat for 6 hours;
(7) the microwave dielectric property of the obtained product is tested by a network analyzerr＝29.72，Qf＝66864GHz， τf＝-23.60×10-6/℃。
Examples 2 to 9
Examples 2-9 the parameters, except for the x value and sintering temperature, were identical to those of example 1, and the main parameters and microwave dielectric properties of the examples of the present invention are detailed in Table 1.
TABLE 1
Figure BDA0002232249070000031

Claims (4)

1. A Ti-base non-stoichiometric microwave dielectric ceramic material is prepared from MgO and TiO2、Nb2O5、ZrO2As a raw material, the target compound has the expression of Mg1+xTi0.9Zr0.1Nb2O8Wherein x is 0.01 to 0.05.
The specific implementation steps are as follows:
(1) mixing MgO and TiO2、Nb2O5、ZrO2Respectively according to the stoichiometric formula Mg1+xTi0.9Zr0.1Nb2O8Mixing x is 0.01-0.05, putting the powder into a polyester tank, adding deionized water and zirconium balls, and performing ball milling for 4-8 hours;
(2) putting the ball-milled raw materials in the step (1) into a drying oven, drying at 80-120 ℃ respectively, and then sieving with a 40-mesh sieve;
(3) putting the powder sieved in the step (2) into a medium-temperature furnace, presintering at 1050 ℃, preserving heat for 2-8 hours, and then sieving by a 40-mesh sieve;
(4) putting the calcined powder in the step (3) into a ball milling tank, adding zirconia balls and deionized water, and carrying out ball milling for 9-12 hours;
(5) putting the ball-milled raw materials in the step (4) into a drying oven, drying, adding 5% polyvinyl alcohol aqueous solution as an adhesive, granulating, sieving with a 80-mesh sieve, and pressing into a green body by using a powder tablet press at a pressure of 4-8 MPa;
(6) and (4) sintering the green body obtained in the step (4) at 1225-1275 ℃, and preserving heat for 2-8 hours to prepare the microwave dielectric ceramic with the medium dielectric constant.
2. The titanium-based non-stoichiometric microwave dielectric ceramic material as claimed in claim 1, wherein step (1) is performed by ball milling using a planetary ball mill with a rotation speed of 400 rpm.
3. A titanium-based non-stoichiometric microwave dielectric ceramic material as claimed in claim 1, wherein the green compact of step (5) has a diameter of 10mm and a thickness of 5 mm.
4. A titanium-based non-stoichiometric microwave dielectric ceramic material as claimed in claim 1, wherein step (6) is sintering in an air atmosphere.
CN201910971617.0A 2019-10-14 2019-10-14 Titanium-based non-stoichiometric microwave dielectric ceramic material Pending CN110818412A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112661509A (en) * 2020-12-24 2021-04-16 电子科技大学 High Q value MgZrNb2O8Microwave-based dielectric ceramic material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04118806A (en) * 1990-05-15 1992-04-20 Sanyo Electric Co Ltd Dielectric ceramic composition for microwave
CN102617141A (en) * 2012-04-05 2012-08-01 天津大学 Intermediate-temperature sintered microwave dielectric ceramic
CN103396117A (en) * 2013-08-01 2013-11-20 天津大学 Low-temperature sintered strontium titanate energy-storing medium ceramic material and preparation method thereof
CN103708834A (en) * 2013-05-24 2014-04-09 济南大学 New method for finely preparing ixiolite structure MgTiNb2O8 microwave dielectric ceramic by using chemical process
CN103951427A (en) * 2014-04-23 2014-07-30 天津大学 Microwave dielectric ceramic material for multilayer ceramic chip capacitors

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04118806A (en) * 1990-05-15 1992-04-20 Sanyo Electric Co Ltd Dielectric ceramic composition for microwave
CN102617141A (en) * 2012-04-05 2012-08-01 天津大学 Intermediate-temperature sintered microwave dielectric ceramic
CN103708834A (en) * 2013-05-24 2014-04-09 济南大学 New method for finely preparing ixiolite structure MgTiNb2O8 microwave dielectric ceramic by using chemical process
CN103396117A (en) * 2013-08-01 2013-11-20 天津大学 Low-temperature sintered strontium titanate energy-storing medium ceramic material and preparation method thereof
CN103951427A (en) * 2014-04-23 2014-07-30 天津大学 Microwave dielectric ceramic material for multilayer ceramic chip capacitors

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Title
XIAOMEI XUE ET AL.: "Phase composition and microwave dielectric properties of Mg-excess MgTiO3 ceramics", 《J MATER SCI: MATER ELECTRON》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112661509A (en) * 2020-12-24 2021-04-16 电子科技大学 High Q value MgZrNb2O8Microwave-based dielectric ceramic material and preparation method thereof

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