CN103214244A - Microwave dielectric ceramics and preparation method thereof - Google Patents

Microwave dielectric ceramics and preparation method thereof Download PDF

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CN103214244A
CN103214244A CN2013101524599A CN201310152459A CN103214244A CN 103214244 A CN103214244 A CN 103214244A CN 2013101524599 A CN2013101524599 A CN 2013101524599A CN 201310152459 A CN201310152459 A CN 201310152459A CN 103214244 A CN103214244 A CN 103214244A
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microwave
preparation
medium ceramics
srco
crystalline phase
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刘林
万丰
王志勇
吴卫华
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Wuhan Hongxin Telecommunication Technologies Co Ltd
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Wuhan Hongxin Telecommunication Technologies Co Ltd
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Abstract

The invention discloses a high-performance microwave dielectric ceramics and a preparation method thereof. The principal crystalline phase is (1-x)CaTiO3-x(LayNd(1-y))GaO3, CaCO3, TiO2, La2O3, Ga2O3 and Nd2O3 are taken as raw materials, and the modified doping agent comprises BaCO3 and SrCO3. The (1-x)CaTiO3-x(LayNd(1-y))GaO3 microwave dielectric ceramics is prepared according to the traditional solid-phase reaction method. The provided microwave dielectric ceramic material has excellent microwave dielectric performance, the relative dielectric constant epsilon r is adjustable between 40 and 45, Q*f is 40000-45000GHz, the resonant frequency temperature coefficient can be continuously adjusted, and the microwave dielectric ceramics can be widely applied to preparing dielectric resonators, filters, duplexers and other microwave devices in the modern communication base station.

Description

A kind of microwave-medium ceramics and preparation method thereof
 
Technical field
The present invention relates to a kind of microwave-medium ceramics that is applied to microwave device and preparation method thereof, belong to the stupalith field.
Background technology
In recent years, modern communications industry develop rapidlys such as mobile communication, satellite communications, Global Positioning System (GPS), Bluetooth technology and wireless lan (wlan).Microwave-medium ceramics has that lossy microwave is low, specific inductivity is high and advantage such as frequency-temperature coefficient is little, the mobility, portability, miniaturization of communication equipment, microminiaturized requirement both can have been satisfied, can satisfy the requirement that in microwave range, has high-performance, high reliability performance characteristics again, obtain paying close attention to widely.
Be applied to the medium dielectric constant microwave medium microwave-medium ceramics in the microwave system, its Essential Performance Requirements is: DIELECTRIC CONSTANT r=30 ~ 50, temperature coefficient of resonance frequency τ f=0 ± 10ppm/ ℃, Q * f 〉=30000GHz.Because CaTiO 3Material has high ε under microwave frequency r, low Q, bigger positive temperature coefficient of resonance frequency τ f, and LaAlO 3Has high ε rBigger negative τ f, thereby both compound preparations can obtain high ε rWith zero τ fMicrowave dielectric material.J.H.Moon etc. study (1-x) CaTiO 3-xLaAlO 3The microwave dielectric property of system pottery.When sintering temperature is 1600 ℃, 0.65CaTiO 3-0.35LaAlO 3Pottery has excellent microwave dielectric properties: ε r=37, Q * f=47000GHz(f=7GHz) and τ f=-2ppm/ ℃.
In order to guarantee microwave-medium ceramics at the industrial production reliability and stability, domestic manufacturer can select to buy synthetic good xCaTiO from Japan and Korea S and American-European producer 3-(1-x) LaAlO 3System microwave-medium ceramics powder has increased the industrial production cost greatly, and has limited its development and use at field microwave-medium devices such as mobile communication.Therefore, be necessary to utilize domestic starting material, the medium dielectric constant microwave medium microwave-medium ceramics of the simple and stable performance of development technology satisfies the needs of microwave system.
Summary of the invention
Technical problem to be solved by this invention provides microwave-medium ceramics of the simple and stable performance of a kind of technology and preparation method thereof.Microwave-medium ceramics of the present invention, preparation technology is simple, can be by domestic raw material preparing, repeatability is good, and the microwave dielectric property excellence.
Microwave-medium ceramics of the present invention comprises principal crystalline phase, and described principal crystalline phase composition is (1-x) CaTiO 3-x (La yNd (1-y)) GaO 3, 0.3≤x≤0.5,0.3≤y≤0.6.
Microwave-medium ceramics of the present invention can also comprise the modification doping agent, and described modification doping agent is BaCO 3And SrCO 3BaCO 3Doping ratio be 0.01%～0.4 % of principal crystalline phase quality, SrCO 3Doping ratio be 0.1 %～0.4 % of principal crystalline phase quality.
This microwave-medium ceramics has dielectric properties preferably: DIELECTRIC CONSTANT r=40 ~ 45, temperature coefficient of resonance frequency τ f=0 ± 10ppm/ ℃, Q * f=40000 ~ 45000GHz.Adopt the microwave-medium ceramics resonator of this pottery preparation, can better be applicable to tracking exchage TM 01Mould, TE 01Mould base station wave filter and base station duplexer.
The present invention also provides the preparation method of above-mentioned microwave-medium ceramics, comprises following concrete steps:
1) takes by weighing CaCO in proportion 3, TiO 2, La 2O 3, Ga 2O 3, Nd 2O 3, mix the back with deionized water and zirconium ball ball milling 3 ~ 10 hours on planetary ball mill;
2) the oven dry back is incubated 3 ~ 6 hours down at 1200 ℃ ~ 1400 ℃, and pre-burning prepares (1-x) CaTiO 3-x (La yNd (1-y)) GaO 3Powder;
3) get BaCO according to doping content 3And SrCO 3, mix with powder after the pre-burning, then according to material: deionized water: the mass ratio of zirconium ball=1:1.2:5 adds deionized water and zirconium ball ball milling 3 ~ 10 hours on planetary ball mill;
4) 60 mesh sieves are crossed in the oven dry of the slurry behind ball milling back, add the PVA binding agent in the powder after sieving and carry out granulation, in 5MPa pressure pressurize compression moulding in 3 minutes;
5) the idiosome after the moulding at 1400 ℃ ~ 1600 ℃ following sintering, wherein temperature rise rate below 650 ℃ is 45 ~ 65 ℃/h, temperature rise rate is 100 ~ 125 ℃/h more than 650 ℃, highest temperature district insulation obtained microwave-medium ceramics in 2 ~ 8 hours.
In the such scheme,
Described BaCO 3, CaCO 3, SrCO 3, TiO 2, La 2O 3, Nd 2O 3, Ga 2O 3Purity be analytical pure.
Described BaCO 3Purity all more than or equal to 99.0%;
Described SrCO 3Purity all more than or equal to 99.0%;
Described CaCO 3Purity all more than or equal to 99.0%;
Described TiO 2Purity all more than or equal to 99.0%;
Described La 2O 3Purity all more than or equal to 99.9%;
Described Ga 2O 3Purity all more than or equal to 99.99%;
Described Nd 2O 3Purity all more than or equal to 99.9%;
Described PVA binding agent is meant that massfraction is the polyvinyl alcohol water solution of 5wt% ~ 10wt%.
Above-mentioned preparation method is by adjusting CaCO 3, TiO 2, La 2O 3, Nd 2O 3, Ga 2O 3Ratio the specific inductivity of material is adjusted to about 47, further add the rare earth oxide BaCO of trace again 3And SrCO 3, improved microwave-medium ceramics Q * f, adjust τ simultaneously fTo 0 ± 10ppm/ ℃.
The inventive method adopts on the conventional solid reaction process basis and prepares stable performance, the high performance microwave media ceramic that repeatability is good.With (1-x) CaTiO 3-xLaAlO 3The high Q value of traditional intermediary electric constant microwave-medium ceramics is compared, the ceramic dielectric constant adjustable (40 ~ 45) of the inventive method preparation, the Q value higher (40000 ~ 45000GHz), temperature coefficient of resonance frequency is ± 10ppm/ ℃ about and adjustable continuously.Can satisfy mobile communication TM 01Mould, TE 01The industrial application demand of mould Jie base station matter wave filter and dielectric duplexer.
Beneficial effect of the present invention is: (1-x) CaTiO not only 3-x (La yNd (1-y)) GaO 3The specific inductivity of microwave-medium ceramics is adjustable in 40 ~ 45 scopes, but also has the characteristic that raw material easily obtains, preparation technology simply reaches high quality factor.This microwave dielectric ceramic materials not leaded (Pb), cadmium (Cd), tribute (Hg), chromium (Cr6 +) wait the objectionable impurities that does not meet environmental protection, help environmental requirement.Preparation method's technical process is simple, process stabilizing and good reproducibility.Can adopt domestic starting material can prepare high performance microwave-medium ceramics.
Description of drawings
Fig. 1 is this patent preparation method's a schema.
Fig. 2 is the X-ray diffraction analysis result of embodiment 2-4.Testing tool is an XRD-7000 type X-ray diffraction analysis tester for the model that Japan produces.
Fig. 3 is the scanning electron microscope picture of embodiment 3.Testing tool is the scanning electronic microscope of JSM-6301 for the model that Japan produces.
Embodiment
Table 1 shows the main component of formation this patent and four specific exampless of different doping contents.
Embodiment 1-5 presses general formula (1-x) CaTiO 3-x (La yNd (1-y)) GaO 3Prepare this patent microwave-medium ceramics through following several steps:
Concrete raw material manufacturer is as follows:
Figure 2013101524599100002DEST_PATH_IMAGE002
1) the principal crystalline phase ratio in table 1 takes by weighing CaCO 3, TiO 2, La 2O 3, Ga 2O 3, Nd 2O 3, mix the back with deionized water and zirconium ball ball milling 6 hours on planetary ball mill;
2) the oven dry back is incubated 6 hours down at 1400 ℃, and pre-burning prepares (1-x) CaTiO 3-x (La yNd (1-y)) GaO 3(0.3≤x≤0.5,0.3≤y≤0.6) powder;
3) get BaCO according to doping content 3And SrCO 3, mix with powder after the pre-burning, then according to material: deionized water: the mass ratio of zirconium ball=1:1.2:5 adds deionized water and zirconium ball ball milling 6 hours on planetary ball mill;
4) 60 mesh sieves are crossed in the oven dry back of the slurry behind the ball milling, according to powder: add the PVA binding agent in the powder of PVA=1g:1.2ml ratio after sieving and carry out granulation, in 5MPa pressure pressurize compression moulding in 3 minutes;
5) the idiosome after the moulding at 1530 ℃ of following sintering, wherein temperature rise rate below 650 ℃ is 45 ~ 65 ℃/h, temperature rise rate is 100 ~ 125 ℃/h more than 650 ℃, highest temperature district insulation obtained dielectric-constant adjustable, higher (1-x) CaTiO of Q * f value in 6 hours 3-x (La yNd (1-y)) GaO 3Microwave-medium ceramics.
6) its preparation method as mentioned above, main flow process is by accompanying drawing 1 explanation.Adopt the Agilent network analyzer to carry out the test of microwave ceramics specific inductivity, adopt Q * f value and the τ that closes chamber method test microwave ceramics with the parallel plate resonance method fValue.
7) adopt XRD-7000 type X-ray diffraction analysis tester that the pottery of embodiment 2 ~ 4 is carried out material phase analysis (as shown in Figure 2), the principal crystalline phase of presentation of results case study on implementation 2 ~ 4 is (1-x) CaTiO 3-x (La yNd (1-y)) GaO 3, and contain a small amount of dephasign.
8) adopt the JSM-6301 scanning electronic microscope that embodiment 3 is carried out Micro-Structure Analysis (as shown in Figure 3), can find out the crystalline-granular texture densification of this patent microwave ceramics, grain-size is bigger, and pore-free.
Table 1 (1-x) CaTiO 3-x (La yNd (1-y)) GaO 3Microwave dielectric ceramic materials is formed
Embodiment The principal crystalline phase proportioning SrCO 3Doping (massfraction) BaCO 3Doping (massfraction)
1 0.58CaTiO 3-0.42（La 0.5Nd 0.5）GaO 3 0 0
2 0.58CaTiO 3-0.42（La 0.5Nd 0.5）GaO 3 0.3% 0.1%
3 0.6CaTiO 3-0.4(La 0.5Nd 0.5)GaO 3 0.3% 0.1%
4 0.64CaTiO 3-0.36(La 0.5Nd 0.5)GaO 3 0.3% 0.1%
5 0.64CaTiO 3-0.36(La 0.4Nd 0.6)GaO 3 0.3% 0.1%
Table 2 (1-x) CaTiO 3-x (La yNd (1-y)) GaO 3The microwave dielectric ceramic materials performance
Embodiment Calcined temperature Sintering temperature ε r Q×f(GHz) τ f（ppm/℃）
1 1400℃ 1530℃ 40.2 40320 -15
2 1400℃ 1530℃ 41.1 44500 2
3 1400℃ 1530℃ 41.9 44200 -1
4 1400℃ 1530℃ 42.7 42700 -2
5 1400℃ 1530℃ 43.1 42000 1

Claims (5)

1. one kind microwave-medium ceramics comprises principal crystalline phase, and described principal crystalline phase composition is (1-x) CaTiO 3-x (La yNd (1-y)) GaO 3, 0.3≤x≤0.5,0.3≤y≤0.6.
2. microwave-medium ceramics according to claim 1 also comprises the modification doping agent, and described modification doping agent is BaCO 3And SrCO 3, BaCO wherein 3Doping content be 0.01%～0.4 % of principal crystalline phase quality, SrCO 3Doping content be 0.1 %～0.4 % of principal crystalline phase quality.
3. the preparation method of the described microwave-medium ceramics of claim 2 is characterized in that, comprises following concrete steps:
1) takes by weighing CaCO in proportion 3, TiO 2, La 2O 3, Ga 2O 3, Nd 2O 3, mix the back with deionized water and zirconium ball ball milling 3 ~ 10 hours on planetary ball mill;
2) the oven dry back is incubated 3 ~ 6 hours down at 1200 ℃ ~ 1400 ℃, and pre-burning prepares (1-x) CaTiO 3-x (La yNd (1-y)) GaO 3Powder;
3) get BaCO according to doping content 3And SrCO 3, mix with powder after the pre-burning, then according to material: deionized water: the mass ratio of zirconium ball=1:1.2:5 adds deionized water and zirconium ball ball milling 3 ~ 10 hours on planetary ball mill;
4) 60 mesh sieves are crossed in the oven dry back of the slurry behind the ball milling, add massfraction in the powder after sieving and be 5% PVA binding agent and carry out granulation, in 5MPa pressure pressurize compression moulding in 3 minutes;
5) the idiosome after the moulding at 1400 ℃ ~ 1600 ℃ following sintering, wherein temperature rise rate below 650 ℃ is 45 ~ 65 ℃/h, temperature rise rate is 100 ~ 125 ℃/h more than 650 ℃, highest temperature district insulation obtained microwave-medium ceramics in 2 ~ 8 hours.
4. preparation method according to claim 3 is characterized in that, described BaCO 3, CaCO 3, SrCO 3, TiO 2, La 2O 3, Nd 2O 3, Ga 2O 3Purity be analytical pure.
5. preparation method according to claim 3 is characterized in that, described PVA binding agent is meant that massfraction is 5% ~ 10% polyvinyl alcohol water solution.
CN2013101524599A 2013-04-27 2013-04-27 Microwave dielectric ceramics and preparation method thereof Pending CN103214244A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104030685A (en) * 2014-04-30 2014-09-10 武汉虹信通信技术有限责任公司 High-Q-value microwave dielectric ceramic and preparation method thereof
CN107311644A (en) * 2017-07-31 2017-11-03 焦作市金川电子科技有限公司 A kind of microwave dielectric ceramic with medium dielectric constant and preparation method thereof
CN109279645A (en) * 2018-11-26 2019-01-29 吉林大学 A kind of cubic phase CaGa2O4The high temperature and high pressure preparation process of compound
CN110511028A (en) * 2019-09-03 2019-11-29 浙江大学 Ultra-low loss microwave-medium ceramics

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1848304A (en) * 2006-05-08 2006-10-18 浙江大学 Mesomeric electric constant laminated microwave dielectric ceramic and producing method thereof
CN1975939A (en) * 2006-12-04 2007-06-06 天津大学 High-dielectric constant microwave dielectric ceramic and producing method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1848304A (en) * 2006-05-08 2006-10-18 浙江大学 Mesomeric electric constant laminated microwave dielectric ceramic and producing method thereof
CN1975939A (en) * 2006-12-04 2007-06-06 天津大学 High-dielectric constant microwave dielectric ceramic and producing method thereof

Non-Patent Citations (1)

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Title
E.A. NENASHEVA ET AL.: "Microwave dielectric properties of ceramics based on CaTiO3-LnMO3 System(Ln-La,Nd;M-Al,Ga)", 《JOURNAL OF THE EUROPEAN CERAMICS SOCIETY》, vol. 23, 31 December 2003 (2003-12-31), pages 2443 - 2448, XP004446258, DOI: doi:10.1016/S0955-2219(03)00188-2 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104030685A (en) * 2014-04-30 2014-09-10 武汉虹信通信技术有限责任公司 High-Q-value microwave dielectric ceramic and preparation method thereof
CN107311644A (en) * 2017-07-31 2017-11-03 焦作市金川电子科技有限公司 A kind of microwave dielectric ceramic with medium dielectric constant and preparation method thereof
CN109279645A (en) * 2018-11-26 2019-01-29 吉林大学 A kind of cubic phase CaGa2O4The high temperature and high pressure preparation process of compound
CN110511028A (en) * 2019-09-03 2019-11-29 浙江大学 Ultra-low loss microwave-medium ceramics
CN110511028B (en) * 2019-09-03 2020-11-03 浙江大学 Ultra-low loss microwave dielectric ceramic

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Application publication date: 20130724