CN105461299A - Temperature stabilization type medium dielectric constant microwave dielectric ceramic NaBiTi<6>O<14> and preparation method thereof - Google Patents

Temperature stabilization type medium dielectric constant microwave dielectric ceramic NaBiTi<6>O<14> and preparation method thereof Download PDF

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CN105461299A
CN105461299A CN201610010918.3A CN201610010918A CN105461299A CN 105461299 A CN105461299 A CN 105461299A CN 201610010918 A CN201610010918 A CN 201610010918A CN 105461299 A CN105461299 A CN 105461299A
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powder
temperature
nabiti
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郑彬宁
覃杏柳
苏聪学
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Guilin University of Technology
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Guilin University of Technology
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/46—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 based on titanium oxides or titanates
    • C04B35/462—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 based on titanium oxides or titanates based on titanates
    • C04B35/475—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 based on titanium oxides or titanates based on titanates based on bismuth titanates
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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Abstract

The invention discloses a temperature stabilization type medium dielectric constant microwave dielectric ceramic NaBiTi<6>O<14> and a preparation method thereof. The preparation method comprises the following steps: 1, weighing and compounding chemical raw materials, namely Na<2>CO<3> powder, Bi<2>O<3> powder and TiO<2> powder, according to the chemical stoichiometric equation NaBiTi<6>O<14>; 2, conducting wet type ball milling mixing on the raw materials as described in step 1 for 12 hours, wherein distilled water serves as a ball milling medium, conducting drying, and then pre-burning the mixture for 6 hours in atmosphere at the temperature of 950 DEG C; 3, adding a binding agent to powder obtained in step 2 for prilling, then conducting compression formation, and finally sintering the mixture for 4 hours in atmosphere at the temperature of 1025-1075 DEG C. A polyvinyl alcohol solution with the mass concentration being 5% is adopted as the binding agent, and the addition amount of polyvinyl alcohol accounts for 3% the total mass of the powder. The ceramic prepared through the preparation method is good in sintering performance at the temperature of 1100 DEG C and below, the dielectric constant reaches 35.7-36.4, the quality factor, namely the Qf value, of the ceramic is as high as 42400-55100 GHz, the temperature coefficient of resonance frequency is low, and extremely high industrial application value is achieved.

Description

A kind of temperature-stable medium dielectric constant microwave medium microwave dielectric ceramic NaBiTi 6o 14and preparation method thereof
Technical field
The present invention relates to dielectric ceramic material, particularly relate to dielectric ceramic material of the microwave devices such as ceramic substrate, 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, the components and parts such as resonator, wave filter, dielectric substrate and medium wave circuit are widely used as in modern communication, it is the key foundation material of modern communication technology, in portable mobile phone, automobile telephone, cordless telephone, telestar susceptor and military radar etc., there is very important application, in the miniaturization, integrated process of modern communication instrument, just playing increasing effect.
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 low dielectric loss tan δ to reduce noise, general requirement Qf>=3000GHz; (3) the temperature factor τ of resonant frequency ?little of as far as possible to ensure the thermostability that device has had, general requirement-10ppm/ DEG C≤τ ?≤+10ppm/ DEG C.From late 1930s, just someone attempts dielectric substance to be applied to microwave technology in the world, and prepares TiO 2microwave dielectric filter, but its temperature coefficient of resonance frequency τ ?too greatly cannot be practical.Since the seventies in last century, start the large-scale development to medium ceramic material, 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 ?≤ 10ppm/ ° of 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 ~ 35, Q=(1 ~ 2) × 10 4(under f>=10GHz), τ ?≈ 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=35 ~ 45, Q=(6 ~ 9) × 10 3(under f=3 ~-4GHz), τ ?≤ 5ppm/ ° of 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 ° of 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 (LowTemperatureCo-firedCeramics, 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 ?) 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, mainly their temperature coefficient of resonance frequency is usually excessive or quality factor are on the low side and cannot application request.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 microtexture and dielectric properties, therefore, in theory also cannot predict its microwave dielectric property 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.Explore and low-temperature sintering can have near-zero resonance frequency temperature coefficient (-10ppm/ DEG C≤τ with exploitation simultaneously ?≤+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.We are to NaBiTi 6o 14, KBiTi 6o 14and LiBiTi 6o 14series compound carried out the research of microwave dielectric property, find that their sintering temperature is lower than 1100 DEG C, wherein KBiTi 6o 14loss is too large and cannot find resonance peak, and LiBiTi 6o 14less but the temperature coefficient of resonance frequency (τ bigger than normal of loss ?=-37ppm/ DEG C) and cannot as practical microwave-medium ceramics.
Summary of the invention
The object of this invention is to provide the application of a kind of titanate as temperature-stable medium dielectric constant microwave medium microwave dielectric ceramic, and prepare the method for this microwave dielectric ceramic.This microwave dielectric ceramic has good thermostability and low-loss, simultaneously can low-temperature sintering.
The chemical constitution of microwave dielectric ceramic material of the present invention is NaBiTi 6o 14.
Preparation method's step of this microwave dielectric ceramic material is:
(1) by chemical feedstocks Na 2cO 3, Bi 2o 3and TiO 2powder is formula NaBiTi stoichiometrically 6o 14weigh batching.
(2) step (1) raw material wet ball-milling is mixed 12 hours, ball-milling medium is distilled water, pre-burning 6 hours in 950 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 1025 ~ 1075 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.
Advantage of the present invention: NaBiTi 6o 14ceramic sintering temperature is low, and raw materials cost is low; Specific inductivity reaches 35.7 ~ 36.4, the temperature factor τ of its resonant frequency ?little, temperature stability is good; Quality factor q f value, up to 42400-55100GHz, 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.
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; Adopt X-ray diffraction analysis to carry out material phase analysis, all samples is one-component ceramic.
This pottery 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 the system such as mobile communication and satellite communications.
Table 1:

Claims (1)

1. titanate is as an application for temperature-stable medium dielectric constant microwave medium microwave dielectric ceramic, it is characterized in that the chemical constitution of described microwave dielectric ceramic is: NaBiTi 6o 14, its specific inductivity is 35.7 ~ 36.4, and temperature coefficient of resonance frequency is-4ppm/ DEG C;
Preparation method's concrete steps of described microwave dielectric ceramic are:
(1) by chemical feedstocks Na 2cO 3, Bi 2o 3and TiO 2powder is formula NaBiTi stoichiometrically 6o 14weigh batching;
(2) step (1) raw material wet ball-milling is mixed 12 hours, ball-milling medium is distilled water, pre-burning 6 hours in 950 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 1025 ~ 1075 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.
CN201610010918.3A 2016-01-09 2016-01-09 Temperature stabilization type medium dielectric constant microwave dielectric ceramic NaBiTi<6>O<14> and preparation method thereof Pending CN105461299A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108558392A (en) * 2018-03-23 2018-09-21 湖北大学 The leadless electronic ceramic material and preparation method of wide operation temperature area low-dielectric loss

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1036777A1 (en) * 1999-03-16 2000-09-20 TDK Corporation Composition of dielectric ceramics and producing method therefor
CN104211391A (en) * 2014-09-27 2014-12-17 桂林理工大学 Low-temperature sintering temperature-stable medium dielectric constant microwave dielectric ceramic Bi3La5Ti7O26 and preparation method thereof
CN104311029A (en) * 2014-09-27 2015-01-28 桂林理工大学 Temperature-stable type microwave dielectric ceramic Bi<2>La<4>Ti<5>O19 having middle dielectric constant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1036777A1 (en) * 1999-03-16 2000-09-20 TDK Corporation Composition of dielectric ceramics and producing method therefor
CN104211391A (en) * 2014-09-27 2014-12-17 桂林理工大学 Low-temperature sintering temperature-stable medium dielectric constant microwave dielectric ceramic Bi3La5Ti7O26 and preparation method thereof
CN104311029A (en) * 2014-09-27 2015-01-28 桂林理工大学 Temperature-stable type microwave dielectric ceramic Bi<2>La<4>Ti<5>O19 having middle dielectric constant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108558392A (en) * 2018-03-23 2018-09-21 湖北大学 The leadless electronic ceramic material and preparation method of wide operation temperature area low-dielectric loss

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