CN105801117A - Temperature-stable microwave dielectric ceramic Ba3SmV3O12 capable of being sintered at low temperature and preparation method of microwave dielectric ceramic Ba3SmV3O12 - Google Patents

Temperature-stable microwave dielectric ceramic Ba3SmV3O12 capable of being sintered at low temperature and preparation method of microwave dielectric ceramic Ba3SmV3O12 Download PDF

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Publication number
CN105801117A
CN105801117A CN201610092898.9A CN201610092898A CN105801117A CN 105801117 A CN105801117 A CN 105801117A CN 201610092898 A CN201610092898 A CN 201610092898A CN 105801117 A CN105801117 A CN 105801117A
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dielectric ceramic
microwave dielectric
ba3smv3o12
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powder
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覃杏柳
苏聪学
郑彬宁
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Guilin University of Technology
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Guilin University of Technology
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    • 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
    • C04B35/495Shaped 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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • 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
    • C04B2235/3205Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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

Abstract

The invention discloses temperature-stable microwave dielectric ceramic Ba3SmV3O12 with a high quality factor capable of being sintered at a low temperature and a preparation method of the microwave dielectric ceramic Ba3SmV3O12. The method comprises the following steps: (1) weighing ingredients, namely powder of analytically pure chemical materials BaCO3, Sm2O3 and V2O5 according to the composition of the Ba3SmV3O12; (2) carrying out wet ball-mill mixing on the raw materials in the step (1) for 12 hours, wherein the ball-mill medium is distilled water; pre-roasting the mixture in an air atmosphere of 900 DEG C for 6 hours after drying; and (3) adding a binder to the powder prepared in the step (2), pelleting and then carrying out compression moulding, and finally sintering the product in the air atmosphere of 950-970 DEG C for 4 hours, wherein a 5% polyvinyl alcohol solution is adopted as the binder; and the adding amount of polyvinyl alcohol accounts for 3% of total mass of the powder. The prepared ceramic is good in sintering property below 1,000 DEG C; the dielectric constant can reach 15.4-16.2; the quality factor Qf value can reach 72,300-88,100GHz; the temperature coefficient of the resonance frequency is small; and the microwave dielectric ceramic Ba3SmV3O12 has great application value in industry.

Description

Low temperature sintering temperature-stable microwave dielectric ceramic Ba3SmV3O12And 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.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 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 Ba3SmV3O12
The preparation method step of this microwave dielectric ceramic material is:
(1) by analytical pure chemical raw material BaCO3、Sm2O3And V2O5Powder press Ba3SmV3O12Composition weigh dispensing.
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is distilled water, at 900 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 950 ~ 970 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: Ba3SmV3O12Ceramic sintering temperature is low, and cost of material is low;Its quality factor q f value is up to 72300-88100GHz, dielectric constant reaches 15.4~16.2, the temperature coefficient τ of its resonant frequencyƒLittle, temperature stability is good; Can be widely used for the manufacture of the microwave devices such as various medium substrate, resonator and wave filter, low temperature co-fired technology and micro-can be met The technology of ripple 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 temperature-stable high quality factor microwave dielectric ceramic, it is characterised in that the chemical group of described microwave dielectric ceramic Become: Ba3SmV3O12
The preparation method of described microwave dielectric ceramic concretely comprises the following steps:
(1) by analytical pure chemical raw material BaCO3、Sm2O3And V2O5Powder press Ba3SmV3O12Composition weigh dispensing;
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is distilled water, 900 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 950 ~ 970 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.
CN201610092898.9A 2016-02-20 2016-02-20 Temperature-stable microwave dielectric ceramic Ba3SmV3O12 capable of being sintered at low temperature and preparation method of microwave dielectric ceramic Ba3SmV3O12 Pending CN105801117A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111153694A (en) * 2020-01-06 2020-05-15 浙江嘉康电子股份有限公司 Microwave dielectric ceramic material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102173764A (en) * 2011-01-11 2011-09-07 桂林理工大学 Bismuth-ferrite-base multiferroic material and preparation method thereof
CN104311031A (en) * 2014-09-27 2015-01-28 桂林理工大学 Low-temperature sinterable microwave dielectric ceramic Ca3Y4V2O14 having low dielectric constant

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102173764A (en) * 2011-01-11 2011-09-07 桂林理工大学 Bismuth-ferrite-base multiferroic material and preparation method thereof
CN104311031A (en) * 2014-09-27 2015-01-28 桂林理工大学 Low-temperature sinterable microwave dielectric ceramic Ca3Y4V2O14 having low dielectric constant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111153694A (en) * 2020-01-06 2020-05-15 浙江嘉康电子股份有限公司 Microwave dielectric ceramic material and preparation method thereof
CN111153694B (en) * 2020-01-06 2022-04-15 浙江嘉康电子股份有限公司 Microwave dielectric ceramic material and preparation method thereof

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