CN102219505A - Microwave tuned composite ceramic material and preparation method thereof - Google Patents

Microwave tuned composite ceramic material and preparation method thereof Download PDF

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Publication number
CN102219505A
CN102219505A CN2011100962173A CN201110096217A CN102219505A CN 102219505 A CN102219505 A CN 102219505A CN 2011100962173 A CN2011100962173 A CN 2011100962173A CN 201110096217 A CN201110096217 A CN 201110096217A CN 102219505 A CN102219505 A CN 102219505A
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microwave
ceramic material
composite ceramic
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徐业彬
赵静媛
何艳艳
刘婷
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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Abstract

The invention discloses a microwave tuned composite ceramic material, which is formed from Mn-doped Ba1-xSrxTiO3 and a mixture. The mole percentage content of the Mn is 0.1-2%. The mass percentage of the Mn-doped Ba1-xSrxTiO3 is 30-95%, wherein x is 0.3-0.7. The mixture is composed of Mg2SiO4 and MgO. The mass percentage of the Mg2SiO4 in the mixture is 1-99%. The invention further discloses a method for preparing the composite ceramic material. The preparation method comprises the following steps of: respectively preparing the M-doped Ba1-xSrxTiO3 and the Mg2SiO4 according to a stoichiometric ratio firstly; ball-milling, discharging, drying and pre-burning the M-doped Ba1-xSrxTiO3 and the Mg2SiO4 to respectively obtain the Mn-doped Ba1-xSrxTiO3 powder and the Mg2SiO4 powder; then, adding Mg2SiO4 and MgO to the Mn-doped Ba1-xSrxTiO3 powder according to the composition; ball-milling, drying, pelleting, forming and removing glue; and finally, sintering at a furnace temperature of 1200-1400 degrees centigrade for 2-4 h to obtain the required material. The material has the characteristics of proper dielectric constant, low dielectric loss, high tuning rate, high performance and low sintering temperature. And the microwave tuned composite ceramic material can be used in microwave devices, such as a phase shifter, a tunable filter, a delay line, an oscillator, a resonator, a phased-array antenna and the like.

Description

A kind of microwave-tuned composite ceramic material and preparation method thereof
Technical field
The invention belongs to the microwave ceramic material technology, be specifically related to the adulterated Ba of a kind of Mn xSr 1-xTiO 3-MgO-Mg 2SiO 4Microwave-tuned composite ceramic material and preparation method thereof.
Background technology
Adjustable filter, retarding line, phase shifter, vibrator, microwave devices such as syntonizer and phased array antenna are the important devices in micro-wave communication field, use but too high cost has limited its wide range of commercial.Low-cost tunable technology will cause the revolution of microwave component and antenna industry.
The specific inductivity of microwave-tuned material can change with impressed voltage.Be applied to the microwave communication field, can change the operating frequency of element by impressed voltage, as allowing a wave filter produce frequency agility, this broadband communications to future is extremely important, because can realize that like this several users is at a common frequency range transmission and received signal.The tuning material of novel microwave can reduce the cost of phased array antenna greatly, with the application that makes phased array antenna by present military extend to civilian.The speed of phased array antenna, precision and reliability are all than corresponding mechanical handling antenna height.
Microwave-tuned material can be used for making phase shifter.Present phase shifter mainly is ferrite phase shifter and semiconductor diode phase shifter.But under high frequency, PIN diode exists loss big, and power is low, needs the logical circuit control phase to move, can not continuous tuning etc. shortcoming; Ferrite is low in the above loss of 3GHz, and power is big, but the costing an arm and a leg of its tuning circuit, and volume is big, heaviness, power consumption is big, only is used for military field, in addition, the loss ratio of ferrite when 1-2GHz is big when 10GHz, is not suitable for cell phone and person-to-person communication service.Ferrite phase shifter is difficult to make two dimensional structure.
The specific inductivity of strontium-barium titanate can change with extra electric field, is a kind of suitable microwave-tuned material.Strontium-barium titanate can be applied to various antennas, and still, the microwave dielectric loss of strontium-barium titanate is too high, need improve material.In addition, too big specific inductivity can cause too big insertion loss, with circuit coupling difficulty.Therefore, how to obtain having moderate specific inductivity, the strontium-barium titanate of higher tuning rate is technological difficulties.
Strontium-barium titanate Ba 1-xSr xTiO 3Composite ceramics has less specific inductivity, dielectric loss and higher tuning rate, wherein with Ba 1-xSr xTiO 3The over-all properties of-MgO is best.Ba 1-xSr xTiO 3-MgO-Mg 2SiO 4Sintering temperature compare Ba 1-xSr xTiO 3The obvious reduction of-MgO, but add Mg 2SiO 4Can cause that microwave dielectric loss increases.
Summary of the invention
The present invention is in order to overcome the deficiencies in the prior art, a kind of microwave-tuned composite ceramic material to be provided, and this material dielectric constant is moderate, and dielectric loss is low, and the tuning rate height is particularly useful for microwave-tuned element; The present invention also provides this preparation methods.
The invention provides a kind of microwave-tuned composite ceramic material, by the adulterated Ba of Mn 1-xSr xTiO 3Constitute with mixture, wherein, the adulterated Ba of described Mn 1-xSr xTiO 3Mass percent be 30-95%, x=0.3-0.7, Mn is with respect to Ba 1-xSr xTiO 3Molar percentage be 0.1-2%, described mixture is by Mg 2SiO 4Constitute Mg with MgO 2SiO 4Mass percent in mixture is 1-99%.
The present invention also provides the method for preparing above-mentioned microwave-tuned composite ceramic material, comprises the steps:
(1) the adulterated Ba of preparation Mn 1-xSr xTiO 3And Mg 2SiO 4Powder;
(2) according to proportioning at the adulterated Ba of Mn 1-xSr xTiO 3Mix pulverous Mg in the powder 2SiO 4And MgO, oven dry after wet ball grinding 6-24 hour;
(3) the polyvinyl alcohol granulation of adding 3-8wt%, compression moulding green compact again in the material after oven dry;
(4) green compact are heated to 400-800 ℃, heat-up rate is incubated 2-4 hour then smaller or equal to 30 ℃/minute, gets rid of the organic substance in the green compact;
(5) sintering in 1200 ℃ of-1400 ℃ of scopes is incubated 2-4 hour again, obtains microwave-tuned composite ceramic material.
Further, above-mentioned steps (1) comprises following substep:
(a) with pulverous BaTiO 3, SrTiO 3And MnCO 3Be mixed in proportion as one group of raw material, with pulverous SiO 2Be mixed in proportion as another group raw material with MgO;
(b) two groups of raw materials are distinguished wet ball grindings 6-24 hour, discharging then, oven dry;
(c) in 1000 ℃ of-1300 ℃ of scopes pre-burning 2-6 hour, obtain the adulterated Ba of Mn respectively 1-xSr xTiO 3And Mg 2SiO 4Powder.
Beneficial effect of the present invention is as follows:
1. composite ceramic material of the present invention is by at Ba 1-xSr xTiO 3The middle Mn that adds suppresses Ba 1-xSr xTiO 3Middle Ti reduction under to the little situation of the influence of specific inductivity and tuning rate, reduces Ba 1-xSr xTiO 3-Mg 2SiO 4The microwave dielectric loss of-MgO, this composite ceramic material can be in 1200 ℃ of-1400 ℃ of scopes sintering, and it is moderate to have a specific inductivity, dielectric loss is low, excellent properties such as tuning rate height have been obtained the result that high-performance and sintering temperature and low have both simultaneously.
2. composite ceramic material of the present invention, its composition is with Ba 1-xSr xTiO 3, Mg 2SiO 4Exist with MgO three-phase composite thing, do not have impurity to exist mutually.
3. composite ceramic material of the present invention can be widely used in variable condenser, adjustable filter, phase shifter, variable delay line, voltage-controlled vibrator, adjustable dielectric resonator, adjustable microwave devices such as adjustable impedance coupling device.Wherein phase shifter is the important devices of phased array antenna, directly determines the cost and the performance of phased array antenna.This material can replace the ferrite of the costliness of using in the phased array antenna, makes the phased array antenna smaller volume, and weight lightens, and it is cheap that price becomes.
4. the preparation method of composite ceramic material of the present invention adopts traditional electronic ceramic technology, and technology is simple, and cost is low, the side effect of material system environment-protecting asepsis.
Description of drawings
The adulterated Ba of Fig. 1 Mn 0.5Sr 0.5TiO 3-MgO-Mg 2SiO 4The XRD spectrum of composite ceramics;
The adulterated Ba of Fig. 2 Mn 0.5Sr 0.5TiO 3-MgO-Mg 2SiO 4The relation curve of the tuning rate of composite ceramics and external dc field intensity.
Embodiment
Below by by example the present invention being described in further detail, but following example only is illustrative, and protection scope of the present invention is not subjected to the restriction of these examples.
Example 1-5:
With pulverous MnCO 3, BaTiO 3, SrTiO 3, SiO 2With MgO be raw material, prepare the adulterated Ba of different content Mn respectively by stoichiometric ratio 1-xSr xTiO 3(x=0.5) and Mg 2SiO 4, in raw material, add dehydrated alcohol or deionized water, be ball-milling medium with agate ball or zirconium dioxide, behind the wet ball grinding 6h, discharging, oven dry, powder is at 1100 ℃ of following pre-burning 2h, obtains the Mn doping content respectively and be 0,0.25,0.5,0.75 and the Ba of 1mol% 1-xSr xTiO 3(x=0.5) and Mg 2SiO 4Powder is with the adulterated Ba of different content Mn 1-xSr xTiO 3(x=0.5), Mg 2SiO 4 Press mass ratio 50 with MgO; Mix at 40: 10 (being respectively example 1-5), wet ball grinding 6h, discharging, oven dry, the polyvinyl alcohol that adopts 5wt% is as the tackiness agent granulation, under the pressure of 150MPa with the pressed by powder moulding; After 600 ℃ of binder removals are handled, in air atmosphere,, obtain the adulterated Ba of Mn in 1330 ℃ of sintering 3h 1-xSr xTiO 3-MgO-Mg 2SiO 4Composite ceramics.Sample after burning till is processed through fine grinding, after the ultrasonic cleaning, goes up silver electrode again, can be used for the dielectric properties test.Cylindrical sample is top electrode not, with Hakki-Coleman method test microwave dielectric property.
The adulterated Ba of Mn 1-xSr xTiO 3-MgO-Mg 2SiO 4Tuning rate and microwave dielectric property under specific inductivity, dielectric loss, 2kV/mm and the 3kV/mm strength of electric field of composite ceramics under 10kHz see Table 1.
The adulterated Ba of table 1 Mn 1-xSr xTiO 3-MgO-Mg 2SiO 4The dielectric properties of composite ceramics
Example Example 1 Example 2 Example 3 Example 4 Example 5
Mn content (mol%) 0 0.25 0.5 0.75 1
Specific inductivity (10kHz) 130.2 124.1 132.2 121.4 118.7
Dielectric loss (10kHz) 0.00065 0.00062 0.00048 0.00042 0.00044
Tuning rate (2kV/mm) 6.4％ 6.5％ 7.37％ 7.33％ 7.9％
Tuning rate (3kV/mm) 11.1％ 11.27％ 12.86％ 12.3％ 13％
Resonant frequency (GHz) 3.42 3.83 3.7 3.82 4.02
Specific inductivity (microwave) 128.03 118.63 127.01 117.81 114.22
Qf(GHz) 475 618 574 570 583
The adulterated Ba of Mn of example 1-5 prescription gained 1-xSr xTiO 3-MgO-Mg 2SiO 4The XRD spectrum of composite ceramics, as shown in Figure 1.Composite ceramic material is by Ba 1-xSr xTiO 3(x=0.5), MgO and Mg 2SiO 4Three phase composites.The Ba of example 1-5 prescription gained 1-xSr xTiO 3-MgO-Mg 2SiO 4The tuning rate of composite ceramics under different DC electric field intensity as shown in Figure 2.Do not compare with there being the adulterated example 1 of Mn, the dielectric loss of composite ceramics under 10kHz reduces, and Qf increases under the microwave frequency.The Qf of example 2 has increased by 30% than example 1, and tuning rate remains unchanged substantially.Example 3,4 and 5 Qf value have also increased more than 20%, and tuning rate even slightly increase.Obviously, at Ba 1-xSr xTiO 3-MgO-Mg 2SiO 4Mix in the composite ceramics Mn can reduce the pottery microwave dielectric loss and tuning rate is constant substantially.
Example 6:Mn molar percentage 0.1%, Ba 1-xSr xTiO 3(x=0.3) mass percent is 30%, Mg 2SiO 4Mass percentage content in mixture is 1%;
Example 7:Mn molar percentage 0.6%, Ba 1-xSr xTiO 3(x=0.45) mass percent is 40%, Mg 2SiO 4Mass percentage content in mixture is 50%;
Example 8:Mn molar percentage 1.5%, Ba 1-xSr xTiO 3(x=0.6) mass percent is 60%, Mg 2SiO 4Mass percentage content in mixture is 80%;
Example 9:Mn molar percentage 2%, Ba 1-xSr xTiO 3(x=0.7) mass percent is 95%, Mg 2SiO 4Mass percentage content in mixture is 99%;
With described material of above-mentioned example 6-9 and stoicheiometry, prepare microwave-tuned composite ceramic material according to following process, resulting material all can reach technique effect of the present invention.
(1) prepares the adulterated Ba of Mn respectively by stoichiometric ratio 1-xSr xTiO 3And Mg 2SiO 4,
Raw material adopts pulverous BaTiO 3, SrTiO 3, MnCO 3, SiO 2And MgO, add dehydrated alcohol or deionized water then, be ball-milling medium with agate ball or zirconium dioxide, behind the ball milling 6h-24h, discharging, oven dry, powder is pre-burning 2h-6h in 1000 ℃ of-1300 ℃ of scopes, obtains the adulterated Ba of Mn respectively 1-xSr xTiO 3And Mg 2SiO 4Powder;
(2) according to forming proportioning, at the adulterated Ba of Mn 1-xSr xTiO 3Mix Mg in the powder 2SiO 4And MgO, add dehydrated alcohol or deionized water then, be ball-milling medium with agate ball or zirconium dioxide, ball milling 6h-24h;
(3) polyvinyl alcohol granulation and the compression moulding green compact of adding 3-8wt% in the mixture after oven dry;
(4) be warmed up to 800 ℃ below the temperature, insulation 2-4 hour, to get rid of the organic substance in the green compact, the heat-up rate of binder removal process is not higher than 30 ℃/min;
(5) green compact sintering in 1200 ℃ of-1400 ℃ of scopes is incubated 2h-4h, obtains the bulk of required excellent performance.
Example among the present invention only is used for that the present invention will be described, does not constitute the restriction to the claim scope, and other substituting of being equal in fact that those skilled in that art can expect are all at protection domain of the present invention.

Claims (3)

1. a microwave-tuned composite ceramic material is characterized in that, it is by the adulterated Ba of Mn 1-xSr xTiO 3Constitute with mixture, wherein, the adulterated Ba of described Mn 1-xSr xTiO 3Mass percent be 30-95%, x=0.3-0.7, Mn is with respect to Ba 1-xSr xTiO 3Molar percentage be 0.1-2%, described mixture is by Mg 2SiO 4Constitute Mg with MgO 2SiO 4Mass percent in mixture is 1-99%.
2. the preparation method of the described microwave-tuned composite ceramic material of claim 1 comprises the steps:
(1) the adulterated Ba of preparation Mn 1-xSr xTiO 3And Mg 2SiO 4Powder;
(2) according to proportioning at the adulterated Ba of Mn 1-xSr xTiO 3Mix pulverous Mg in the powder 2SiO 4And MgO, oven dry after wet ball grinding 6-24 hour;
(3) the polyvinyl alcohol granulation of adding 3-8wt%, compression moulding green compact again in the material after oven dry;
(4) green compact are heated to 400-800 ℃, heat-up rate is incubated 2-4 hour then smaller or equal to 30 ℃/minute, gets rid of the organic substance in the green compact;
(5) sintering in 1200 ℃ of-1400 ℃ of scopes is incubated 2-4 hour again, obtains microwave-tuned composite ceramic material.
3. the preparation method of microwave-tuned composite ceramic material according to claim 2 is characterized in that, step (1) comprises following substep:
(a) with pulverous BaTiO 3, SrTiO 3And MnCO 3Be mixed in proportion as one group of raw material, with pulverous SiO 2Be mixed in proportion as another group raw material with MgO;
(b) two groups of raw materials are distinguished wet ball grindings 6-24 hour, discharging then, oven dry;
(c) in 1000 ℃ of-1300 ℃ of scopes pre-burning 2-6 hour, obtain the adulterated Ba of Mn respectively 1-xSr xTiO 3And Mg 2SiO 4Powder.
CN2011100962173A 2011-04-18 2011-04-18 Microwave tuned composite ceramic material and preparation method thereof Pending CN102219505A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN108975907A (en) * 2018-09-05 2018-12-11 天津大学 The method for improving barium titanate dielectric material resistance to reduction is adulterated by transition-metal ions
CN109020537A (en) * 2018-09-05 2018-12-18 天津大学 A kind of anti-reduction low-loss type barium phthalate base dielectric material
CN115925401A (en) * 2022-11-10 2023-04-07 华中科技大学 Low-dielectric silicate microwave dielectric ceramic material and preparation method thereof

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WO2002059059A2 (en) * 2001-01-24 2002-08-01 Paratek Microwave, Inc. Electronically tunable, low-loss ceramic materials including a tunable dielectric phase and multiple metal oxide phases

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN108975907A (en) * 2018-09-05 2018-12-11 天津大学 The method for improving barium titanate dielectric material resistance to reduction is adulterated by transition-metal ions
CN109020537A (en) * 2018-09-05 2018-12-18 天津大学 A kind of anti-reduction low-loss type barium phthalate base dielectric material
CN115925401A (en) * 2022-11-10 2023-04-07 华中科技大学 Low-dielectric silicate microwave dielectric ceramic material and preparation method thereof
CN115925401B (en) * 2022-11-10 2023-07-25 华中科技大学 Low-dielectric silicate microwave dielectric ceramic material and preparation method thereof

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Application publication date: 20111019