CN105859277A - High-quality-factor microwave dielectric ceramic Li2Cu3V2O9 which can be sintered at low temperature and preparation method thereof - Google Patents

High-quality-factor microwave dielectric ceramic Li2Cu3V2O9 which can be sintered at low temperature and preparation method thereof Download PDF

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CN105859277A
CN105859277A CN201610434276.XA CN201610434276A CN105859277A CN 105859277 A CN105859277 A CN 105859277A CN 201610434276 A CN201610434276 A CN 201610434276A CN 105859277 A CN105859277 A CN 105859277A
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dielectric ceramic
powder
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microwave dielectric
preparation
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徐敏育
李纯纯
方维双
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Guilin University of Technology
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Guilin University of Technology
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C04B35/01—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
    • C04B35/45—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 copper oxide or solid solutions thereof with other oxides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • 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
    • C04B2235/3203—Lithium oxide or oxide-forming salts thereof
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Abstract

The invention discloses a high-quality-factor microwave dielectric ceramic Li2Cu3V2O9 which can be sintered at low temperature and a preparation method thereof. The preparation method comprises the steps that 1, Li2CO3 CuO and V2O5 raw powder with the purity of 99.9% or above (weight percentage) is weighed according to the composition of the Li2Cu3V2O9 for burdening; 2, the raw material in the step 1 is subjected to wet ball milling and mixing for 12 hours, and a ball milling medium is distilled water and is presintered in the air atmosphere of 750 DEG C for 6 hours after being dried; 3, a binder is added in the powder prepared in the step 2, granulation is performed, then pressing is performed for forming, and finally the powder is sintered in the air atmosphere of 800-850 DEG C for 4 hours, wherein the binder is a polyvinyl alcohol solution with the mass concentration of 5%, and the adding amount of the polyvinyl alcohol accounts for 3% of the total mass of the powder. The prepared ceramic is good in sintering at the temperature of 850 DEG C or below, a dielectric constant is up to 12.5-13.3, a quality factor Qf value is up to 93000-151000 GHz, a resonant frequency temperature coefficient is small, and the high-quality-factor microwave dielectric ceramic has a great application value in the industry.

Description

Low temperature sintering high quality factor microwave dielectric ceramic Li2Cu3V2O9And preparation Method
Technical field
The present invention relates to dielectric ceramic material, particularly relate to for manufacturing ceramic substrate, the resonance that microwave frequency uses Dielectric ceramic materials of microwave device such as device and wave filter 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.It is mainly used in the microwave communication equipment such as direct broadcasting satellite of f >=8 GHz as being situated between Matter 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 have good heat stability and low-loss, low temperature sintering is ultralow simultaneously Dielectric constant microwave dielectric ceramic material and preparation method thereof.
The chemical composition of the microwave dielectric ceramic material of the present invention is high quality factor.
The preparation method step of this microwave dielectric ceramic material is:
(1) be 99.9%(percentage by weight by purity) more than Li2CO3, CuO and V2O5Starting powder press Li2Cu3V2O9's Composition weighs dispensing.
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is distilled water, at 750 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 800 ~ 850 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: Li2Cu3V2O9Ceramic sintering temperature is low, and cost of material is low；Its quality factor q f value is up to 93000-151000 GHz, dielectric constant reaches 12.5～13.3, 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 substrate, dielectric resonator and wave filter, can meet low temperature co-fired technology and The technology of microwave 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 medium substrate, resonator and wave filter, can meet shifting The technology of the systems such as dynamic communication and satellite communication needs.
Table 1:

Claims (1)

1. a high quality factor temperature-stable ultralow dielectric microwave dielectric ceramic, it is characterised in that described micro-wave dielectric The chemical composition of pottery is: Li2Cu3V2O9；
The preparation method of described microwave dielectric ceramic concretely comprises the following steps:
(1) be 99.9%(percentage by weight by purity) more than Li2CO3, CuO and V2O5Starting powder press Li2Cu3V2O9Group Become to weigh dispensing；
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is distilled water, 750 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 800 ~ 850 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.
CN201610434276.XA 2016-06-18 2016-06-18 High-quality-factor microwave dielectric ceramic Li2Cu3V2O9 which can be sintered at low temperature and preparation method thereof Pending CN105859277A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104744041A (en) * 2015-03-26 2015-07-01 桂林理工大学 Temperature stable type microwave dielectric ceramic Li2Cu2Nb8O23 with low dielectric constant
CN104891991A (en) * 2015-05-23 2015-09-09 桂林理工大学 Low-dielectric-constant microwave dielectric ceramic SrLi2Cu2V8O24 and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104744041A (en) * 2015-03-26 2015-07-01 桂林理工大学 Temperature stable type microwave dielectric ceramic Li2Cu2Nb8O23 with low dielectric constant
CN104891991A (en) * 2015-05-23 2015-09-09 桂林理工大学 Low-dielectric-constant microwave dielectric ceramic SrLi2Cu2V8O24 and preparation method thereof

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