CN106242530A - Ultralow dielectric microwave dielectric ceramic Li2in4ge3o13 - Google Patents

Ultralow dielectric microwave dielectric ceramic Li2in4ge3o13 Download PDF

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CN106242530A
CN106242530A CN201610583410.2A CN201610583410A CN106242530A CN 106242530 A CN106242530 A CN 106242530A CN 201610583410 A CN201610583410 A CN 201610583410A CN 106242530 A CN106242530 A CN 106242530A
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dielectric
hours
microwave
powder
binding agent
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徐敏育
段炼
卢锋奇
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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
    • 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
    • C04B35/622—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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    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
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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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    • 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
    • C04B2235/3287—Germanium oxides, germanates or oxide forming salts thereof, e.g. copper germanate
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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
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Abstract

The invention discloses a kind of low-loss temperature-stabilized ultralow dielectric microwave dielectric ceramic Li2In4Ge3O13And preparation method thereof.(1) by Li that purity is more than 99.9% (percentage by weight)2CO3、In2O3And GeO2Starting powder press Li2In4Ge3O13Composition weigh dispensing；(2) by step (1) raw material wet ball-milling mix 12 hours, ball-milling medium is distilled water, after drying in 1100 DEG C of air atmosphere pre-burning 6 hours；(3) after adding binding agent pelletize in the powder that step (2) prepares, re-compacted molding, finally sinter 4 hours in 1150～1200 DEG C of air atmosphere；Described binding agent uses mass concentration to be the poly-vinyl alcohol solution of 5%, and the addition of polyvinyl alcohol accounts for the 3% of powder gross mass.Pottery prepared by the present invention sinters well below 1200 DEG C, and dielectric constant reaches 6.4～7.2, and its quality factor q f value is up to 79000 96000GHz, and temperature coefficient of resonance frequency is little, industrially has great using value.

Description

Ultralow dielectric microwave dielectric ceramic Li2In4Ge3O13
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 >=3000GHz；(3) the temperature coefficient τ of resonant frequencyfThe least to ensure the heat that device has had Stability ,-10ppm/ DEG C≤τ of general requirementf≤+10ppm/℃.Just have tried to electricity from late 1930s in the world Dielectric material is applied to microwave technology, and prepares TiO2Microwave dielectric filter, but its temperature coefficient of resonance frequency τfToo big and Cannot be practical.Since the seventies in last century, start the large-scale development to medium ceramic material, according to being relatively situated between Electric constant εrSize different from use frequency range, generally can will have been developed that and the microwave-medium ceramics developed be divided into 4 Class.
(1) ultralow dielectric microwave dielectric ceramic, main representative is Al2O3-TiO2、Y2BaCuO5、MgAl2O4With Mg2SiO4Deng, its εr≤ 20, quality factor q × f >=50000GHz, τf≤10ppm/℃.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 f >=10GHz), τf≈0.In the microwave communication equipments such as the direct broadcasting satellite being mainly used in f >=8GHz humorous as medium Shake 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), τf≤5ppm/℃.Main use As dielectric resonance device in microwave military radar in 4～8GHz frequency ranges and communication system.
(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 DEG C, it is impossible to directly and the low-melting-point metal such as Ag and Cu Burn 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 system materials Material has carried out exploring widely and studying, and mainly uses devitrified glass or glassceramic composites system, because of low melting point glass Glass has of a relatively high dielectric loss mutually, and the existence of glass phase substantially increases the dielectric loss of material.Therefore develop without glass 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 τfIt is that the relation of mutually restriction is (see literary composition between) Offer: the restricting relation between microwave dielectric ceramic materials dielectric properties, Zhu Jianhua, Liang Fei, Wang little Hong, Lv Wenzhong, electronic component with Material, phase March the 3rd in 2005), meet three performance requirements and the single-phase microwave-medium ceramics of low temperature sintering is considerably less, main Cannot application request if their temperature coefficient of resonance frequency is the most excessive or quality factor are on the low side.At present to micro- The research major part of ripple media ceramic is the summary of experience drawn by great many of experiments, does not but have complete theory micro-to illustrate See the relation of structure and dielectric properties, therefore, the most also cannot predict its resonance frequency from the composition of compound with structure The microwave dielectric properties such as rate temperature coefficient and quality factor, which greatly limits low temperature co-fired technology and microwave multilamellar The development of device.Explore and low-temperature sintering can have near-zero resonance frequency temperature coefficient (-10ppm/ DEG C≤τ with exploitation simultaneouslyf≤ + 10ppm/ DEG C) it is that those skilled in the art thirst for solving always but are difficult to all the time with the microwave dielectric ceramic of higher figure of merit The difficult problem succeeded.We are to consisting of Li2In4Ge3O13With Li2In4Si3O13Pottery carried out sintering and micro-wave dielectric Performance study, finds that their sintering temperature is less than 1200 DEG C, wherein Li2In4Ge3O13There is near-zero resonance frequency temperature coefficient With high quality factor, Li2In4Si3O13Pottery is quasiconductor, and its dielectric loss is big and does not has resonance peak, therefore cannot be as can be real With the microwave-medium ceramics changed.
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 ultralow dielectric microwave be situated between Electroceramics material and preparation method thereof.
The chemical composition of the microwave dielectric ceramic material of the present invention is Li2In4Ge3O13。
The preparation method step of this microwave dielectric ceramic material is:
(1) by Li that purity is more than 99.9% (percentage by weight)2CO3、In2O3And GeO2Starting powder press Li2In4Ge3O13Composition weigh dispensing.
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is distilled water, big at 1100 DEG C after drying Pre-burning 6 hours in gas atmosphere.
(3) after adding binding agent pelletize in the powder that step (2) prepares, re-compacted molding, finally 1150～ 1200 DEG C of air atmosphere sinter 4 hours；Described binding agent uses mass concentration to be the poly-vinyl alcohol solution of 5%, polyethylene Alcohol addition accounts for the 3% of powder gross mass.
Advantages of the present invention: Li2In4Ge3O13Ceramic sintering temperature is relatively low, and cost of material is low；Its quality factor q f value is up to 79000-96000GHz, dielectric constant reaches 6.4～7.2, the temperature coefficient τ of its resonant frequencyfLittle, temperature stability is good；Can It is widely used in the manufacture of the microwave devices such as various medium substrate, 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 system Preparation 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: Li2In4Ge3O13；
The preparation method of described microwave dielectric ceramic concretely comprises the following steps:
(1) by Li that purity is more than 99.9% (percentage by weight)2CO3、In2O3And GeO2Starting powder press Li2In4Ge3O13 Composition weigh dispensing；
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is distilled water, at 1100 DEG C of air gas 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 1150～1200 DEG C Air atmosphere sinters 4 hours；Described binding agent uses mass concentration to be the poly-vinyl alcohol solution of 5%, and polyvinyl alcohol adds Amount accounts for the 3% of powder gross mass.
CN201610583410.2A 2016-07-22 2016-07-22 Ultralow dielectric microwave dielectric ceramic Li2in4ge3o13 Pending CN106242530A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110627480A (en) * 2019-09-01 2019-12-31 桂林理工大学 MgO-Al2O3-GeO2Preparation method of ternary system microwave dielectric material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105541300A (en) * 2015-12-19 2016-05-04 桂林理工大学 Temperature-stable ultralow dielectric constant microwave dielectric ceramic Li2B2Ge2O8 and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105541300A (en) * 2015-12-19 2016-05-04 桂林理工大学 Temperature-stable ultralow dielectric constant microwave dielectric ceramic Li2B2Ge2O8 and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110627480A (en) * 2019-09-01 2019-12-31 桂林理工大学 MgO-Al2O3-GeO2Preparation method of ternary system microwave dielectric material
CN110627480B (en) * 2019-09-01 2022-07-22 桂林理工大学 MgO-Al2O3-GeO2Preparation method of ternary system microwave dielectric material

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Application publication date: 20161221