CN104311030A - Temperature stabilization type microwave dielectric ceramic with ultralow dielectric constant, and preparation method of microwave dielectric ceramic - Google Patents

Temperature stabilization type microwave dielectric ceramic with ultralow dielectric constant, and preparation method of microwave dielectric ceramic Download PDF

Info

Publication number
CN104311030A
CN104311030A CN201410554933.5A CN201410554933A CN104311030A CN 104311030 A CN104311030 A CN 104311030A CN 201410554933 A CN201410554933 A CN 201410554933A CN 104311030 A CN104311030 A CN 104311030A
Authority
CN
China
Prior art keywords
dielectric ceramic
microwave dielectric
temperature
hours
microwave
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410554933.5A
Other languages
Chinese (zh)
Other versions
CN104311030B (en
Inventor
方亮
李威
孙宜华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yidu Botong Electronic Co ltd
Original Assignee
China Three Gorges University CTGU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Three Gorges University CTGU filed Critical China Three Gorges University CTGU
Priority to CN201410554933.5A priority Critical patent/CN104311030B/en
Publication of CN104311030A publication Critical patent/CN104311030A/en
Application granted granted Critical
Publication of CN104311030B publication Critical patent/CN104311030B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227Lanthanum oxide or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3239Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

The invention discloses a temperature stabilization type microwave dielectric ceramic La2Bi5V3O18 with ultralow dielectric constant, and a preparation method of the microwave dielectric ceramic La2Bi5V3O18; the microwave dielectric ceramic La2Bi5V3O18 can be sintered at low temperature. The preparation method comprises the steps of (1) weighing the original powder of La2O3, Bi2O3 and V2O5 according to the composition of La2Bi5V3O18, and blending, wherein the purities of La2O3, Bi2O3 and V2O5 are over 99.9% (by weight percent); (2) carrying out mixing on the raw materials in the step (1) by wet ball milling for 12 hours, wherein the ball-milling medium is distilled water; drying the mixture, and then presintering for 6 hours in the atmosphere at the temperature of 650 DEG C; and (3) feeding a bonding agent into the powder prepared in the step (2), carrying out granulation, molding by pressing, and finally sintering for 4 hours in the atmosphere at the temperature of 700-750 DEG C, wherein a polyvinyl alcohol solution with the mass concentration of 5% is adopted as the bonding agent, and the feeding amount of the polyvinyl alcohol accounts for 3% of the total mass of the powder. The microwave dielectric ceramic La2Bi5V3O18 prepared by the method can be well sintered at the temperature of 700-750 DEG C, has the dielectric constant reaching 19.4-19.8, has the quality factor (Qf) value reaching up to 51000-66000GHz, and is low in temperature coefficient of resonance frequency, thus having great application value in industry.

Description

A kind of temperature-stable ultralow dielectric microwave dielectric ceramic and preparation method thereof
Technical field
The present invention relates to microwave dielectric ceramic material, particularly relate to dielectric ceramic material of the microwave devices such as medium substrate, Ceramic Resonator and the wave filter used for the manufacture of microwave frequency and preparation method thereof.
Background technology
Microwave dielectric ceramic refers to and to be applied in microwave frequency band (mainly UHF and SHF frequency range) circuit as dielectric material and to complete the pottery of one or more functions, resonator is widely used as in modern communication, wave filter, the components and parts such as dielectric substrate and medium wave circuit, it is the key foundation material of modern communication technology, at portable mobile phone, automobile telephone, cordless telephone, there is very important application the aspects such as telestar susceptor and military radar, in the miniaturization of modern communication instrument, increasing effect is just being played in integrated process.
Be applied to the dielectric ceramic of microwave frequency band, the requirement of following dielectric characteristics should be met: (1) seriation DIELECTRIC CONSTANT ε rto adapt to the requirement of different frequency and different application occasion; (2) high quality factor q value or dielectric loss tan δ to reduce noise, general requirement Qf>=3000GHz; (3) the temperature factor τ of resonant frequency flittle of as far as possible to ensure the thermostability that device has had, general requirement-10/ DEG C≤τ f≤+10ppm/ DEG C.From late 1930s, just someone attempts dielectric substance to be applied to microwave technology in the world.
According to relative permittivity ε rsize from use frequency range different, usually the microwave-medium ceramics be developed and developing can be divided into 4 classes.
(1) ultralow dielectric microwave dielectric ceramic, main representative is Al 2o 3-TiO 2, Y 2baCuO 5, MgAl 2o 4and Mg 2siO 4deng, its ε r≤ 20, quality factor q × f>=50000GHz, τ f≤ 10ppm/ DEG C.Be mainly used in microwave base plate and high-end microwave device.
(2) low ε rwith the microwave dielectric ceramic of high q-factor, mainly BaO-MgO-Ta 2o 5, BaO-ZnO-Ta 2o 5or BaO-MgO-Nb 2o 5, BaO-ZnO-Nb 2o 5system or the composite system MWDC material between them.Its ε r=20 ~ 30, Q=(1 ~ 2) × 10 4(under f>=10GHz), τ f≈ 0.Be mainly used in the microwave communication equipments such as the direct broadcasting satellite of f >=8GHz as dielectric resonance device.
(3) medium ε rwith the microwave dielectric ceramic of Q value, mainly with BaTi 4o 9, Ba 2ti 9o 20(Zr, Sn) TiO 4deng the MWDC material for base, its ε r=30 ~ 50, Q=(6 ~ 9) × 10 3(under f=3 ~-4GHz), τ f≤ 5ppm/ DEG C.Be mainly used in microwave military radar in 4 ~ 8GHz range of frequency and communication system as dielectric resonance device.
(4) high ε rand the microwave dielectric ceramic that Q value is lower, be mainly used in civilian mobile communcations system in 0.8 ~ 4GHz range of frequency, this is also the emphasis of microwave dielectric ceramic research.Since the eighties, the people such as Kolar, Kato in succession find and have studied perovskite-like tungsten bronze type BaO-Ln 2o 3-TiO 2series (Ln=La, Sm, Nd or Pr etc. are called for short BLT system), complex perovskite structure CaO-Li 2o-Ln 2o 3-TiO 2series, lead base series material, Ca 1-xln 2x/3tiO 3be contour ε rmicrowave dielectric ceramic, the wherein BaO-Nd of BLT system 2o 3-TiO 2material dielectric constant reaches 90, lead base series (Pb, Ca) ZrO 3specific inductivity reaches 105.
The sintering temperature of these material systems is generally higher than 1300 DEG C above, can not directly and the low melting point metal such as Ag and Cu burn formation laminated ceramic capacitor altogether.In recent years, along with LTCC Technology (Low Temperature Co-fired Ceramics, the requirement of development LTCC) and the development of microwave multilayer device, researchist both domestic and external has carried out exploring widely and studying to some low fever's system materials, mainly adopt devitrified glass or glassceramic composites system, because low melting glass has relatively high dielectric loss mutually, the existence of glassy phase substantially increases the dielectric loss of material.Therefore development is the emphasis of current research without the low fired microwave dielectric ceramic material of glassy phase.
Can in the process of low fired microwave dielectric ceramic materials in exploration and development of new, the material systems such as the Li based compound that intrinsic sintering temperature is low, Bi based compound, tungstate architecture compound and tellurate architecture compound get the attention and research, but due to three performance index (ε of microwave dielectric ceramic rwith Qf and τ f) between be that the relation of mutually restriction is (see document: the restricting relation between microwave dielectric ceramic materials dielectric properties, Zhu Jianhua, Liang Fei, Wang little Hong, Lv Wenzhong, electronic component and material, phase March the 3rd in 2005), meet three performance requriementss and the single-phase microwave-medium ceramics of low temperature sintering is considerably less, their the temperature coefficient of resonance frequency usually too large quality factor of excessive or loss is on the low side and cannot production application.Current is the summary of experience drawn by great many of experiments to the research major part of microwave-medium ceramics, but complete theory is not had to set forth the relation of its microtexture and dielectric properties, therefore, in theory also cannot predict whether it has the numerical range of microwave dielectric property and the performance perameter such as temperature coefficient of resonance frequency and quality factor from the composition of compound and structure, which greatly limits the development of low temperature co-fired technology and microwave multilayer device.Therefore, explore and develop low-temperature sintering can have near-zero resonance frequency temperature coefficient (τ simultaneously f≤ 10ppm/ DEG C) be that those skilled in the art thirst for solving always but are difficult to the difficult problem that succeeds all the time with the microwave dielectric ceramic of higher figure of merit (Qf>=50000GHz).We are to consisting of La 2bi 5v 3o 18, Nd 2bi 5v 3o 18, Sm 2bi 5v 3o 18, Pr 2bi 5v 3o 18vanadate carried out the research of microwave dielectric property, wherein find that their sintering temperature is lower than 900 DEG C, but only have La 2bi 5v 3o 18there is near-zero resonance frequency temperature coefficient and high quality factor, the temperature coefficient of resonance frequency (>30ppm/ DEG C) all bigger than normal of other composition pottery
Summary of the invention
The object of this invention is to provide and a kind of there is low-loss and good thermostability, simultaneously low temperature sintering ultralow dielectric microwave dielectric ceramic material and preparation method thereof.
The chemical constitution of microwave dielectric ceramic material of the present invention is La 2bi 5v 3o 18.
Preparation method's step of this microwave dielectric ceramic material is:
(1) by purity be the La of more than 99.9% (weight percent) 2o 3, Bi 2o 3and V 2o 5starting powder press La 2bi 5v 3o 18composition weigh batching.
(2) step (1) raw material wet ball-milling is mixed 12 hours, ball-milling medium is distilled water, pre-burning 6 hours in 650 DEG C of air atmosphere after oven dry.
(3) in the powder that step (2) is obtained, binding agent is added and after granulation, then compression moulding, finally in 700-750 DEG C of air atmosphere, sinter 4 hours; Described binding agent adopts mass concentration to be the polyvinyl alcohol solution of 5%, and polyvinyl alcohol addition accounts for 3% of powder total mass.
Pottery prepared by the present invention is good at 700 ~ 750 DEG C of sintering, and specific inductivity reaches 19.1 ~ 19.8, the temperature factor τ of its resonant frequency flittle, temperature stability is good; Its quality factor q f value, up to 51000-66000GHz, can be widely used in the manufacture of the microwave devices such as various medium substrate, resonator and wave filter, can meet the technology needs of low temperature co-fired technology and microwave multilayer device, industrially have great using value.
Embodiment
Embodiment:
Table 1 shows 3 specific embodiments and microwave dielectric property thereof that form different sintering temperature of the present invention.Its preparation method is described above, carries out the evaluation of microwave dielectric property by cylindrical dielectric resonator method.
This pottery can be widely used in the manufacture of the microwave devices such as various medium substrates, can meet the technology needs of the system such as mobile communication and satellite communications.
Table 1:

Claims (2)

1. a temperature-stable ultralow dielectric microwave dielectric ceramic, is characterized in that, the chemical constitution of described microwave dielectric ceramic is: La 2bi 5v 3o 18.
2. a preparation method for temperature-stable ultralow dielectric microwave dielectric ceramic, is characterized in that, concrete steps are:
(1) be 99.9%(weight percent by purity) more than La 2o 3, Bi 2o 3and V 2o 5starting powder press La 2bi 5v 3o 18composition weigh batching;
(2) step (1) raw material wet ball-milling is mixed 12 hours, ball-milling medium is distilled water, pre-burning 6 hours in 650 DEG C of air atmosphere after oven dry;
(3) in the powder that step (2) is obtained, binding agent is added and after granulation, then compression moulding, finally in 700-750 DEG C of air atmosphere, sinter 4 hours; Described binding agent adopts mass concentration to be the polyvinyl alcohol solution of 5%, and polyvinyl alcohol addition accounts for 3% of powder total mass.
CN201410554933.5A 2014-10-17 2014-10-17 A kind of temperature-stable ultralow dielectric microwave dielectric ceramic and preparation method thereof Active CN104311030B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410554933.5A CN104311030B (en) 2014-10-17 2014-10-17 A kind of temperature-stable ultralow dielectric microwave dielectric ceramic and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410554933.5A CN104311030B (en) 2014-10-17 2014-10-17 A kind of temperature-stable ultralow dielectric microwave dielectric ceramic and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104311030A true CN104311030A (en) 2015-01-28
CN104311030B CN104311030B (en) 2015-11-11

Family

ID=52366380

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410554933.5A Active CN104311030B (en) 2014-10-17 2014-10-17 A kind of temperature-stable ultralow dielectric microwave dielectric ceramic and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104311030B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106187133A (en) * 2016-07-24 2016-12-07 桂林理工大学 Temperature-stable ultralow dielectric microwave dielectric ceramic LiBi3si2o9

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1342622A (en) * 2001-10-10 2002-04-03 浙江大学 Ceramics as low-loss microwave medium
CN1581368A (en) * 2003-08-07 2005-02-16 松下电器产业株式会社 Dielectric ceramic composition and ceramic electronic component employing the same
CN102603292A (en) * 2012-03-20 2012-07-25 广西新未来信息产业股份有限公司 Composite oxide used for sintering microwave dielectric ceramics at low temperature

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1342622A (en) * 2001-10-10 2002-04-03 浙江大学 Ceramics as low-loss microwave medium
CN1581368A (en) * 2003-08-07 2005-02-16 松下电器产业株式会社 Dielectric ceramic composition and ceramic electronic component employing the same
CN102603292A (en) * 2012-03-20 2012-07-25 广西新未来信息产业股份有限公司 Composite oxide used for sintering microwave dielectric ceramics at low temperature

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KOK-WAN TAY ET AL.,: "Effect of Bi2O3 additives on sintering and microwave dielectric behavior of La(Mg0.5Ti0.5)O3 ceramics", 《CERAMICS INTERNATIONAL》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106187133A (en) * 2016-07-24 2016-12-07 桂林理工大学 Temperature-stable ultralow dielectric microwave dielectric ceramic LiBi3si2o9

Also Published As

Publication number Publication date
CN104311030B (en) 2015-11-11

Similar Documents

Publication Publication Date Title
CN104211397A (en) Temperature stable type microwave dielectric ceramic Nb2VY3O12 with ultralow dielectric constant
CN104311017A (en) Vanadium-based temperature-stable low-temperature sintering microwave dielectric ceramic and preparation method thereof
CN104311031B (en) Low temperature sintering dielectric constant microwave ceramic medium Ca 3y 4v 2o 14
CN104844211A (en) Temperature-stable medium-dielectric constant microwave dielectric ceramic Li2SmNbO5
CN104496422A (en) Low-temperature sintered temperature-stable microwave dielectric ceramic Li3Mg2BO5 and preparation method thereof
CN104261826A (en) Microwave dielectric ceramic ZnY3VO8 with ultralow dielectric constant
CN104844210A (en) Temperature-stable low-dielectric constant microwave dielectric ceramic CaLaV3O10
CN104261832A (en) Low-temperature-sintering ultralow-dielectric-constant microwave dielectric ceramic BaY4V2O12
CN105198403A (en) Ultralow-dielectric-constant microwave dielectric ceramic Li3ZnBi5O11 and preparation method thereof
CN104876570A (en) High-quality factor low-dielectric constant microwave dielectric ceramic BaLi3La3W2O13
CN104891992A (en) High-quality-factor low-dielectric-constant microwave dielectric ceramic BaLiBiW2O9
CN104817324A (en) Temperature-stable microwave dielectric ceramics Li<2>LaVO<5> with low dielectric constants
CN104761261A (en) Temperature-stable ultralow-dielectric-constant microwave dielectric ceramic LiMgV5O14
CN104311022A (en) Microwave dielectric ceramic Li2Bi3V7O23 with ultralow dielectric constant and preparation method thereof
CN105565809A (en) High-quality-factor temperature-stable type low-dielectric-constant microwave dielectric ceramic Cu2Mg2V2O9
CN105272241A (en) Temperature-stable microwave dielectric ceramic LiCaVO4 with low dielectric constant
CN104844209A (en) Temperature-stable low-dielectric constant microwave dielectric ceramic Li2NdV5O15
CN104311029A (en) Temperature-stable type microwave dielectric ceramic Bi<2>La<4>Ti<5>O19 having middle dielectric constant
CN104628384A (en) Low-loss temperature-stable type middle-dielectric-constant microwave dielectric ceramic LiBi2NbO6
CN104261824A (en) Low-temperature-sintering ultralow-dielectric-constant microwave dielectric ceramic Bi2ZnW3O13
CN104311018A (en) Ultralow-dielectric-constant microwave dielectric ceramic and preparation method thereof
CN104261827A (en) Low-temperature sinterable microwave dielectric ceramic Bi2MgW5O19 with low dielectric constant
CN104311030A (en) Temperature stabilization type microwave dielectric ceramic with ultralow dielectric constant, and preparation method of microwave dielectric ceramic
CN105565802A (en) Temperature stabilization type low dielectric constant microwave dielectric ceramic Mg4BiVO5
CN105236954A (en) Microwave dielectric ceramic Li3MgBi5O10 with ultralow dielectric constant and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20221118

Address after: No. 23, Wangcheng Road, Yaojiadian Town, Yidu City, Yichang City, Hubei Province 443399

Patentee after: YIDU BOTONG ELECTRONIC Co.,Ltd.

Address before: 443002 No. 8, University Road, Yichang, Hubei

Patentee before: CHINA THREE GORGES University