CN105777077A - High-quality-factor low-dielectric constant microwave dielectric ceramic Ca3MgTiGe3O12 and preparing method thereof - Google Patents

High-quality-factor low-dielectric constant microwave dielectric ceramic Ca3MgTiGe3O12 and preparing method thereof Download PDF

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CN105777077A
CN105777077A CN201610088003.4A CN201610088003A CN105777077A CN 105777077 A CN105777077 A CN 105777077A CN 201610088003 A CN201610088003 A CN 201610088003A CN 105777077 A CN105777077 A CN 105777077A
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dielectric ceramic
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卢锋奇
李纯纯
邓酩
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Guilin University of Technology
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Guilin University of Technology
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
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Abstract

The invention discloses high-quality-factor temperature stabilization type low-dielectric constant microwave dielectric ceramic Ca3MgTiGe3O12 and a preparing method thereof.The preparing method comprises the steps that firstly, original CaCO3 powder with the purity being 99.9wt% or above, original MgO powder with the purity being 99.9wt% or above and original GeO2 powder with the purity being 99.9wt% or above are weighed for compounding according to constitutes of Ca3MgTiGe3O12; secondly, the raw materials in the first step are subjected to wet-type ball-milling mixing for 12 hours, the ball-milling medium is distilled water, and after drying, the mixture is presintered for 6 hours under the 850-DEG C atmosphere; thirdly, binder is added into the powder obtained in the second step, after granulating, compression molding is conducted, and finally sintering is conducted under the 950-1,000 DEG C atmosphere for 4 hours, wherein a 5% polyvinyl alcohol solution is adopted as the binder, and the adding amount of the polyvinyl alcohol is 3% of the total mass of the powder.The prepared ceramic is good in sintering at the temperature of 950 DEG C or below, the dielectric constant reaches 23.1-23.9, the quality factor Qf value of the prepared ceramic is up to 87,000-141,000 GHz, the temperature coefficient of resonance frequency is small, and the ceramic has great application value in industry.

Description

High quality factor dielectric constant microwave dielectric ceramic Ca3MgTiGe3O12And preparation Method
Technical field
The present invention relates to dielectric ceramic material, particularly relate to for manufacturing ceramic resonator and the filter that microwave frequency uses 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 range) circuit as dielectric material And complete the pottery of one or more functions, modern communication is widely used as resonator, wave filter, dielectric substrate and medium The components and parts such as wave circuit, are the key foundation materials of modern communication technology, in portable mobile phone, automobile telephone, nothing The aspect such as rope phone, television satellite accepter and military radar has highly important application, small-sized at modern communication instrument Change, integrated during just playing increasing effect.
It is applied to the dielectric ceramic of microwave frequency band, should meet the requirement of following dielectric property: (1) seriation DIELECTRIC CONSTANT εr To adapt to different frequency and the requirement of different application occasion;(2) high quality factor q value or low dielectric loss tan δ are to reduce Noise, typically requires Qf >=3000 GHz;(3) the temperature coefficient τ of resonant frequencyƒThe least to ensure what device had had Heat stability, general requirement-10 ppm/DEG C≤τƒ≤+10 ppm/℃.Just have tried to from late 1930s in the world Dielectric substance is applied to microwave technology, and prepares TiO2Microwave dielectric filter, but its temperature coefficient of resonance frequency τƒ Too greatly cannot be practical.Since the seventies in last century, the large-scale development to medium ceramic material, root are started According to relative dielectric constant εrSize from use frequency range different, generally can will have been developed that and developing microwave-medium pottery Porcelain is divided into 4 classes.
(1) ultralow dielectric microwave dielectric ceramic, main representative is Al2O3-TiO2、Y2BaCuO5、MgAl2O4With Mg2SiO4Deng, its εr≤ 20, quality factor q × f >=50000GHz, τƒ≤10 ppm/°C.It is mainly used in microwave base plate and height End 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 material between them.Its εr=20～35, Q=(1～2) × 104(under the GHz of f >=10), τƒ≈0.As medium in the microwave communication equipments such as the direct broadcasting satellite being mainly used in f >=8 GHz Resonating device.
(3) medium εrWith the microwave dielectric ceramic of Q-value, it is mainly with BaTi4O9、Ba2Ti9O20(Zr, Sn) TiO4Etc. for The MWDC material of base, its εr=35 ~ 45, Q=(6～9) × 103(under f=3～-4GHz), τƒ≤5 ppm/°C.It is mainly used in 4 ～8 in microwave military radar in GHz frequency range and communication system as dielectric resonance device.
(4) high εrAnd the microwave dielectric ceramic that Q-value is relatively low, in being mainly used in 0.8～4GHz frequency range, civilian movement is led to News system, this is also the emphasis of microwave dielectric ceramic research.Since the eighties, Kolar, Kato et al. in succession find and have studied Perovskite-like tungsten bronze type BaO Ln2O3—TiO2Series (Ln=La, Sm, Nd or Pr etc. are called for short BLT system), composite perofskite Structure C aO Li2O—Ln2O3—TiO2Series, lead base series material, Ca1-xLn2x/3TiO3It is contour εrMicrowave dielectric ceramic, The wherein BaO Nd of BLT system2O3—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 ° of C, it is impossible to directly golden with the low melting point such as Ag and Cu Belong to burning altogether and form multilayer ceramic capacitor.In recent years, along with LTCC Technology (Low Temperature Co-fired Ceramics, LTCC) development and microwave multilayer device development requirement, research worker both domestic and external is to some low grade fever's systems Material has carried out exploring widely and studying, and mainly uses devitrified glass or glassceramic composites system, because of low melting point Glass has of a relatively high dielectric loss mutually, and the existence of glass phase substantially increases the dielectric loss of material.Therefore nothing is developed The low fired microwave dielectric ceramic material of glass phase is the emphasis of current research.
Explore novel with exploitation can be during low fired microwave dielectric ceramic materials, the Li base that intrinsic sintering temperature is low The material systems such as compound, Bi based compound, tungstates architecture compound and tellurate architecture compound get the attention with Research, but due to three performance indications (ε of microwave dielectric ceramicrWith Q f and τƒBetween) be mutually restriction relation (see Document: the restricting relation between microwave dielectric ceramic materials dielectric properties, Zhu Jianhua, Liang Fei, Wang little Hong, Lv Wenzhong, electronics unit Part and material, phase March the 3rd in 2005), satisfied three performance requirements and the single-phase microwave-medium ceramics of low temperature sintering are very Few, mainly their temperature coefficient of resonance frequency is the most excessive or quality factor are on the low side and cannot application request.Mesh The front research major part to microwave-medium ceramics is the summary of experience drawn by great many of experiments, does not but have complete theory Illustrate the relation of microstructure and dielectric properties, therefore, the most also cannot predict it from the composition of compound with structure The microwave dielectric property such as temperature coefficient of resonance frequency and quality factor, which greatly limits low temperature co-fired technology and micro- The development of ripple multilayer device.Explore with exploitation can low-temperature sintering have simultaneously near-zero resonance frequency temperature coefficient (-10 ppm/ ℃≤τƒ≤+10 ppm/ DEG C) with the microwave dielectric ceramic of higher figure of merit be those skilled in the art thirst for solving always but All the time the difficult problem succeeded it is difficult to.
Summary of the invention
It is an object of the invention to provide and a kind of there is good heat stability and low-loss, simultaneously low Jie of low temperature sintering Electric constant microwave dielectric ceramic material and preparation method thereof.
The chemical composition of the microwave dielectric ceramic material of the present invention is Ca3MgTiGe3O12。
The preparation method step of this microwave dielectric ceramic material is:
(1) be 99.9%(percentage by weight by purity) more than CaCO3、MgO、TiO2And GeO2Starting powder press Ca3MgTiGe3O12Composition weigh dispensing.
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is distilled water, at 850 DEG C of air after drying Pre-burning 6 hours in atmosphere.
(3), after adding binding agent pelletize in the powder that step (2) prepares, re-compacted molding, finally at 900 ~ 950 DEG C Air atmosphere sinters 4 hours；Described binding agent uses mass concentration to be the poly-vinyl alcohol solution of 5%, polyvinyl alcohol addition Account for the 3% of powder gross mass.
Advantages of the present invention: Ca3MgTiGe3O12Ceramic sintering temperature is low, and cost of material is low；Its quality factor q f value is up to 87000-141000GHz, dielectric constant reaches 23.1～23.9, the temperature coefficient τ of its resonant frequencyƒLittle, temperature stability Good；Can be widely used for the manufacture of the microwave devices such as various dielectric resonator and wave filter, low temperature co-fired technology and microwave can be met The technology of multilayer device needs.
Detailed description of the invention
Embodiment:
Table 1 shows 3 specific embodiments and the microwave dielectric property thereof of the different sintering temperatures constituting the present invention.Its preparation side Method as it has been described above, carry out the evaluation of microwave dielectric property by cylindrical dielectric resonator method.
This pottery can be widely used for the manufacture of the microwave devices such as various dielectric resonator and wave filter, can meet mobile communication Need with the technology of the system such as satellite communication.
Table 1:

Claims (1)

1. a high quality factor temperature-stable dielectric constant microwave dielectric ceramic, it is characterised in that described micro-wave dielectric is made pottery The chemical composition of porcelain is: Ca3MgTiGe3O12；
The preparation method of described microwave dielectric ceramic concretely comprises the following steps:
(1) be 99.9%(percentage by weight by purity) more than CaCO3、MgO、TiO2And GeO2Starting powder press Ca3MgTiGe3O12Composition weigh dispensing；
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is distilled water, 850 DEG C of air atmosphere after drying Middle pre-burning 6 hours；
(3), after adding binding agent pelletize in the powder that step (2) prepares, re-compacted molding, finally at 900 ~ 950 DEG C of air Atmosphere sinters 4 hours；Described binding agent uses mass concentration to be the poly-vinyl alcohol solution of 5%, and polyvinyl alcohol addition accounts for powder The 3% of end gross mass.
CN201610088003.4A 2016-02-17 2016-02-17 High-quality-factor low-dielectric constant microwave dielectric ceramic Ca3MgTiGe3O12 and preparing method thereof Pending CN105777077A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111517789A (en) * 2020-04-29 2020-08-11 桂林理工大学 Low-dielectric microwave dielectric ceramic material and preparation method thereof
CN112194493A (en) * 2020-10-15 2021-01-08 桂林理工大学 Low dielectric constant microwave dielectric ceramic and preparation method thereof
CN112408980A (en) * 2020-10-31 2021-02-26 桂林理工大学 Low-dielectric-constant microwave dielectric ceramic with adjustable resonant frequency temperature coefficient and preparation method thereof
CN113651600A (en) * 2021-08-19 2021-11-16 桂林理工大学 Germanate microwave dielectric ceramic with low dielectric constant and high quality factor and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435342A (en) * 2013-08-20 2013-12-11 桂林理工大学 Titanate microwave dielectric ceramic Ba2Ti5Zn(1-x)MgxO13 and preparation method thereof
CN103864414A (en) * 2014-01-28 2014-06-18 江苏南瓷绝缘子股份有限公司 Low-dielectric-constant microwave dielectric ceramic and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435342A (en) * 2013-08-20 2013-12-11 桂林理工大学 Titanate microwave dielectric ceramic Ba2Ti5Zn(1-x)MgxO13 and preparation method thereof
CN103864414A (en) * 2014-01-28 2014-06-18 江苏南瓷绝缘子股份有限公司 Low-dielectric-constant microwave dielectric ceramic and preparation method thereof

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MATJAZ VALANT ET AL: "Glass-free low-temperature cofired ceramics: calcium germanates, silicates and tellurates", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111517789A (en) * 2020-04-29 2020-08-11 桂林理工大学 Low-dielectric microwave dielectric ceramic material and preparation method thereof
CN111517789B (en) * 2020-04-29 2022-06-14 桂林理工大学 Low-dielectric microwave dielectric ceramic material and preparation method thereof
CN112194493A (en) * 2020-10-15 2021-01-08 桂林理工大学 Low dielectric constant microwave dielectric ceramic and preparation method thereof
CN112194493B (en) * 2020-10-15 2022-08-05 桂林理工大学 Low dielectric constant microwave dielectric ceramic and preparation method thereof
CN112408980A (en) * 2020-10-31 2021-02-26 桂林理工大学 Low-dielectric-constant microwave dielectric ceramic with adjustable resonant frequency temperature coefficient and preparation method thereof
CN113651600A (en) * 2021-08-19 2021-11-16 桂林理工大学 Germanate microwave dielectric ceramic with low dielectric constant and high quality factor and preparation method thereof

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Application publication date: 20160720