CN105503157B - Temperature-stable dielectric constant microwave dielectric ceramic Ba3Li2Ge2O8And preparation method thereof - Google Patents

Temperature-stable dielectric constant microwave dielectric ceramic Ba3Li2Ge2O8And preparation method thereof Download PDF

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CN105503157B
CN105503157B CN201610023221.XA CN201610023221A CN105503157B CN 105503157 B CN105503157 B CN 105503157B CN 201610023221 A CN201610023221 A CN 201610023221A CN 105503157 B CN105503157 B CN 105503157B
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dielectric ceramic
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dielectric constant
binding agent
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CN105503157A (en
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方亮
李威
李东升
孙宜华
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Yidu Botong Electronic Co ltd
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China Three Gorges University CTGU
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Abstract

The invention discloses a kind of high quality factor temperature-stable dielectric constant microwave dielectric ceramic Ba3Li2Ge2O8And preparation method thereof.(1) it is BaCO more than 99.9% (percentage by weight) by purity3、Li2CO3And GeO2Starting powder press Ba3Li2Ge2O8Composition weigh dispensing；(2) by step (1) raw material wet ball-milling mix 12 hours, ball-milling medium is distilled water, after drying in 820 DEG C of air atmospheres pre-burning 6 hours；(3) after binding agent is added in powder made from step (2) and is granulated, re-compacted shaping is finally sintered 4 hours in 870~920 DEG C of air atmospheres；Described binding agent uses mass concentration for 5% poly-vinyl alcohol solution, and the addition of polyvinyl alcohol accounts for the 3% of powder gross mass.Ceramics prepared by the present invention are sintered well below 920 DEG C, and dielectric constant reaches 21.3~22.5, and its quality factor q f values are up to 79000 137000GHz, and temperature coefficient of resonance frequency is small, industrially there is great application value.

Description

Temperature-stable dielectric constant microwave dielectric ceramic Ba3Li2Ge2O8And its prepare Method
Technical field
The present invention relates to dielectric ceramic material, more particularly to for manufacturing ceramic resonator and the filter that microwave frequency is used Dielectric ceramic materials of microwave device such as ripple device and preparation method thereof.
Background technology
Microwave dielectric ceramic refers to be applied in microwave frequency band (mainly UHF and SHF frequency ranges) circuit as dielectric material And the ceramics of one or more functions are completed, it is widely used as resonator, wave filter, dielectric substrate and medium in modern communication The components such as wave circuit, are the key foundation materials of modern communication technology, in portable mobile phone, automobile telephone, nothing There is highly important application in terms of rope phone, television satellite recipient and military radar, in the small-sized of modern communication instrument Change, it is integrated during just playing increasing effect.
Applied to the dielectric ceramic of microwave frequency band, the requirement of following dielectric property should be met：(1) seriation permittivity εr To adapt to the requirement of different frequency and different application occasion；(2) high quality factor q value or low dielectric loss tan δ are to reduce Noise, typically requires Qf >=3000GHz；(3) the temperature coefficient τ of resonant frequencyfIt is as small as possible to ensure heat that device has had Stability, general -10ppm/ DEG C of requirement≤τf≤+10ppm/℃.Just had tried to electricity from late 1930s in the world Dielectric material is applied to microwave technology, and prepares TiO2Microwave dielectric filter, but its temperature coefficient of resonance frequency τfIt is too big and Can not be practical.Since the seventies in last century, the large-scale development to medium ceramic material is started, according to relative Jie Electric constant εrSize with using frequency range difference, generally the microwave-medium ceramics for having been developed that He developing can be divided into 4 Class.
(1) ultralow dielectric microwave dielectric ceramic, main representative is Al2O3-TiO2、Y2BaCuO5、MgAl2O4With Mg2SiO4Deng its εr≤ 20, quality factor q × f >=50000GHz, τf≤10ppm/℃.It is mainly used in microwave base plate and height Hold microwave device.
(2) low εrWith the microwave dielectric ceramic of high q-factor, mainly BaO-MgO-Ta2O5,BaO-ZnO-Ta2O5Or BaO- MgO-Nb2O5,BaO-ZnO-Nb2O5System or the hybrid system MWDC materials between them.Its εr=20~35, Q=(1~2) ×104(under f >=10GHz), τf≈0.It is mainly used in humorous as medium in the microwave communication equipments such as f >=8GHz direct broadcasting satellite Shake device.
(3) medium εrWith the microwave dielectric ceramic of Q values, it is mainly with BaTi4O9、Ba2Ti9O20(Zr, Sn) TiO4Etc. for The MWDC materials of base, its εr=35~45, Q=(6~9) × 103(under f=3~-4GHz), τf≤5ppm/℃.It is main to use Dielectric resonator device is used as in the microwave military radar and communication system in 4~8GHz frequency ranges.
(4) high εrAnd the relatively low microwave dielectric ceramic of Q values, it is mainly used in civilian movement in 0.8~4GHz frequency ranges and leads to News system, this is also the emphasis of microwave dielectric ceramic research.Since the eighties, Kolar, Kato et al. have found and have studied in succession Perovskite-like tungsten bronze type BaO-Ln2O3—TiO2Serial (Ln=La, Sm, Nd or Pr etc., abbreviation BLT systems), composite perofskite Structure C aO-Li2O—Ln2O3—TiO2Series, lead base series material, Ca1-xLn2x/3TiO3It is contour εrMicrowave dielectric ceramic, Wherein BaO-Nd of BLT systems2O3—TiO2Material dielectric constant reaches 90, lead base series (Pb, Ca) ZrO3Dielectric constant reaches To 105.
The sintering temperature of the above material system is generally greater than 1300 DEG C, it is impossible to directly with the low-melting-point metal such as Ag and Cu Burn altogether and form multilayer ceramic capacitor.In recent years, with LTCC Technology (Low Temperature Co-fired Ceramics, LTCC) development and microwave multilayer device development requirement, researcher both domestic and external is to some low fever's system materials Material has carried out extensive exploration and research, mainly using devitrified glass or glassceramic composite system, because of low melting point glass Glass mutually has of a relatively high dielectric loss, and the presence of glass phase substantially increases the dielectric loss of material.Therefore develop without glass Low fever's microwave dielectric ceramic materials of glass phase are the emphasis of current research.
Explore with develop it is new can be during low fever's microwave dielectric ceramic material, the low Li bases of intrinsic sintering temperature The material systems such as compound, Bi based compounds, tungstates system compound and tellurate system compound get the attention with Research, but be due to three performance indications (ε of microwave dielectric ceramicrWith Qf and τf) between be the relation mutually restricted (see text Offer：Restricting relation between microwave dielectric ceramic materials dielectric properties, Zhu Jianhua, Liang Fei, Wang Xiaohong, Lv Wenzhong, electronic component with Material, phase March the 3rd in 2005), meet three performance requirements and the single-phase microwave-medium ceramics of low temperature sintering are considerably less, it is main If their temperature coefficient of resonance frequency generally excessive or quality factor it is relatively low and can not application request.At present to micro- Most of research of ripple media ceramic is the summary of experience drawn by many experiments, but illustrates micro- without complete theory The relation of structure and dielectric properties is seen, therefore, its resonance frequency can not be also predicted from the composition and structure of compound in theory The microwave dielectric property such as rate temperature coefficient and quality factor, which greatly limits low temperature co-firing technology and microwave multilayer The development of device.Exploration and exploitation can low-temperature sintering there is (- 10ppm/ DEG C≤τ of near-zero resonance frequency temperature coefficient simultaneouslyf≤ + 10ppm/ DEG C) with the microwave dielectric ceramic of higher figure of merit it is that those skilled in the art thirst for solving but being all the time difficult to always The problem succeeded.
The content of the invention
There is good heat endurance and low-loss it is an object of the invention to provide a kind of, be situated between while low temperature sintering is low Electric constant microwave dielectric ceramic material and preparation method thereof.
The chemical composition of the microwave dielectric ceramic material of the present invention is Ba3Li2Ge2O8。
The preparation method step of this microwave dielectric ceramic material is：
(1) it is BaCO more than 99.9% (percentage by weight) by purity3、Li2CO3And GeO2Starting powder press Ba3Li2Ge2O8Composition weigh dispensing.
(2) step (1) raw material wet ball-milling is mixed 12 hours, ball-milling medium is distilled water, in 820 DEG C of air after drying Pre-burning 6 hours in atmosphere.
(3) after binding agent is added in powder made from step (2) and is granulated, re-compacted shaping, finally 870~920 Sintered 4 hours in DEG C air atmosphere；Described binding agent uses mass concentration for 5% poly-vinyl alcohol solution, and polyvinyl alcohol adds Dosage accounts for the 3% of powder gross mass.
Advantages of the present invention：Ba3Li2Ge2O8Ceramic sintering temperature is low, and cost of material is low；Its quality factor q f values are up to 79000-137000GHz, dielectric constant reaches 21.3~22.5, the temperature coefficient τ of its resonant frequencyfIt is small, temperature stability It is good；The manufacture of the microwave devices such as various dielectric resonators and wave filter is can be widely used for, low temperature co-firing technology and microwave can be met The technology of multilayer device needs.
Embodiment
Embodiment：
Table 1 shows 3 specific embodiments and its microwave dielectric property for constituting the different sintering temperatures of the present invention.It is made Preparation Method is as described above, carry out the evaluation of microwave dielectric property with cylindrical dielectric resonator method.
This ceramics can be widely used for the manufacture of the microwave devices such as various dielectric resonators and wave filter, can meet mobile communication Needed with the technology of the system such as satellite communication.
Table 1：

Claims (1)

1. a kind of high quality factor temperature-stable dielectric constant microwave dielectric ceramic, it is characterised in that the micro-wave dielectric pottery The chemical composition of porcelain is：Ba3Li2Ge2O8；
The preparation method of the microwave dielectric ceramic is concretely comprised the following steps：
（1）By the BaCO that purity is more than 99.9wt%3、Li2CO3And GeO2Starting powder press Ba3Li2Ge2O8Composition weigh Dispensing；
（2）By step（1）Raw material wet ball-milling is mixed 12 hours, and ball-milling medium is distilled water, in 820 DEG C of air atmospheres after drying Middle pre-burning 6 hours；
（3）In step（2）After binding agent is added in obtained powder and is granulated, re-compacted shaping, finally in 900 DEG C of air atmospheres Middle sintering 4 hours；Described binding agent uses mass concentration for 5% poly-vinyl alcohol solution, and poly-vinyl alcohol solution addition accounts for powder The 3% of last gross mass.
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CN106116552A (en) * 2016-06-26 2016-11-16 桂林理工大学 Li3gaSiO5application as low-loss temperature-stabilized microwave dielectric ceramic
CN106187105A (en) * 2016-07-19 2016-12-07 桂林理工大学 High quality factor temperature-stable dielectric constant microwave dielectric ceramic Li2baMgGeO5

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103396120A (en) * 2013-08-05 2013-11-20 桂林理工大学 Low-temperature sinterable molybdenum-based microwave dielectric ceramic Ba4Li2Mo2O11
CN104671776A (en) * 2015-02-04 2015-06-03 桂林理工大学 Low-loss low-dielectric-constant microwave dielectric ceramic Li2Ba3Ti8O20 and preparation method thereof

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN103396120A (en) * 2013-08-05 2013-11-20 桂林理工大学 Low-temperature sinterable molybdenum-based microwave dielectric ceramic Ba4Li2Mo2O11
CN104671776A (en) * 2015-02-04 2015-06-03 桂林理工大学 Low-loss low-dielectric-constant microwave dielectric ceramic Li2Ba3Ti8O20 and preparation method thereof

Non-Patent Citations (1)

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Low-temperature sintering of Ba6-3xSm8+2xTi18O54 microwave dielectric ceramics by B2O3 and GeO2 addition;Yutaka Ota等;《Journalof the European Ceramic Society》;20031002;第24卷(第6期);第1756页右栏最后一段至第1757页左栏第1段、第1760页右栏第1段 *

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