CN105948729A - Temperature-stable ultralow-dielectric-constant microwave dielectric ceramic LiBSiO4 - Google Patents

Temperature-stable ultralow-dielectric-constant microwave dielectric ceramic LiBSiO4 Download PDF

Info

Publication number
CN105948729A
CN105948729A CN201610441830.7A CN201610441830A CN105948729A CN 105948729 A CN105948729 A CN 105948729A CN 201610441830 A CN201610441830 A CN 201610441830A CN 105948729 A CN105948729 A CN 105948729A
Authority
CN
China
Prior art keywords
temperature
dielectric
hours
powder
purity
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.)
Pending
Application number
CN201610441830.7A
Other languages
Chinese (zh)
Inventor
方亮
段炼
苏和平
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.)
Guilin University of Technology
Original Assignee
Guilin University of Technology
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 Guilin University of Technology filed Critical Guilin University of Technology
Priority to CN201610441830.7A priority Critical patent/CN105948729A/en
Publication of CN105948729A publication Critical patent/CN105948729A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C04B35/01—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
    • C04B35/16—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 silicates other than clay
    • 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
    • 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
    • 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
    • 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
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • 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
    • 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
    • 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
    • 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

Landscapes

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

Abstract

The invention discloses an application and preparing method of temperature-stable ultralow-dielectric-constant microwave dielectric ceramic with borate LiBSiO4 as a material capable of low-temperature sintering. The preparing method includes the steps that 1, original powder of Li2CO3, original powder of H3BO3 and original powder of SiO2 are weighed and prepared according to composition of the LiBSiO4, wherein the purity of the Li2CO3, the purity of the H3BO3 and the purity of the SiO2 are 99.9% (weight percentage) or above; 2, the raw materials in the step 1 are subjected to wet ball-mill mixing for 12 hours, a ball-milling medium is distilled water, and the product is dried to be presintered for 6 hours in the air atmosphere of 800 DEG C; 3, a binding agent is added into the powder prepared in the step 2, and pelleting is carried out, then pressing molding is carried out, and finally, the product is sintered for 4 hours in the air atmosphere of 850 DEG C to 900 DEG C; the binding agent is a polyvinyl alcohol solution with the mass concentration of 5%, and the additive amount of polyvinyl alcohol is 3% of the total powder mass. The ceramic prepared with the method is good in sintering at the temperature of 900 DEG C or below, the dielectric constant ranges from 8.9 to 9.5, the quality factor (Qf) value is up to 93,000 GHz to 142,000 GHz, the temperature coefficient of resonance frequency is small, and the huge application value is achieved in the industry.

Description

Temperature-stable ultralow dielectric microwave dielectric ceramic LiBSiO4
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 LiBSiO4。
The preparation method step of this microwave dielectric ceramic material is:
(1) be 99.9%(percentage by weight by purity) more than Li2CO3、H3BO3And SiO2Starting powder press LiBSiO4Group Become to weigh dispensing.
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is distilled water, at 800 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 850 ~ 900 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: LiBSiO4Ceramic sintering temperature is low, and cost of material is low；Its quality factor q f value is up to 93000-142000GHz, dielectric constant reaches 8.9～9.5, 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 borate is as the application of temperature-stable ultralow dielectric microwave dielectric ceramic, it is characterised in that described boron The chemical composition of hydrochlorate is: LiBSiO4；
Described boratory preparation method concretely comprises the following steps:
(1) be 99.9%(percentage by weight by purity) more than Li2CO3、H3BO3And SiO2Starting powder press LiBSiO4Group Become to weigh dispensing；
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is distilled water, 800 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 850 ~ 900 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.
CN201610441830.7A 2016-06-20 2016-06-20 Temperature-stable ultralow-dielectric-constant microwave dielectric ceramic LiBSiO4 Pending CN105948729A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610441830.7A CN105948729A (en) 2016-06-20 2016-06-20 Temperature-stable ultralow-dielectric-constant microwave dielectric ceramic LiBSiO4

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610441830.7A CN105948729A (en) 2016-06-20 2016-06-20 Temperature-stable ultralow-dielectric-constant microwave dielectric ceramic LiBSiO4

Publications (1)

Publication Number Publication Date
CN105948729A true CN105948729A (en) 2016-09-21

Family

ID=56906151

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610441830.7A Pending CN105948729A (en) 2016-06-20 2016-06-20 Temperature-stable ultralow-dielectric-constant microwave dielectric ceramic LiBSiO4

Country Status (1)

Country Link
CN (1) CN105948729A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107129278A (en) * 2017-04-26 2017-09-05 浙江嘉康电子股份有限公司 The ultralow high Q that is situated between microwave dielectric ceramic materials and its preparation technology

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103130496A (en) * 2013-03-25 2013-06-05 桂林理工大学 Low-dielectric-constant microwave dielectric ceramic LiAlSi2O6 and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103130496A (en) * 2013-03-25 2013-06-05 桂林理工大学 Low-dielectric-constant microwave dielectric ceramic LiAlSi2O6 and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107129278A (en) * 2017-04-26 2017-09-05 浙江嘉康电子股份有限公司 The ultralow high Q that is situated between microwave dielectric ceramic materials and its preparation technology

Similar Documents

Publication Publication Date Title
CN104628369B (en) A kind of ultralow dielectric temperature-stable microwave dielectric ceramic Li2mg4si4o13
CN104557019B (en) Sintered at ultra low temperature temperature-stable microwave dielectric ceramic LiBiB2o5and preparation method thereof
CN106187160A (en) Low-loss temperature-stabilized microwave dielectric ceramic LiGaSn3o8
CN104671783B (en) Low-loss temperature stabilized microwave dielectric ceramic LiMg3NbWO9
CN105777077A (en) High-quality-factor low-dielectric constant microwave dielectric ceramic Ca3MgTiGe3O12 and preparing method thereof
CN106116550A (en) A kind of silicate Li2siO3application as temperature-stable high quality factor microwave dielectric ceramic
CN104446433B (en) Temperature-stable ultralow dielectric microwave dielectric ceramic Li3al2p3o12
CN104628384B (en) Low-loss temperature-stabilized medium dielectric constant microwave medium microwave dielectric ceramic LiBi2nbO6
CN105948729A (en) Temperature-stable ultralow-dielectric-constant microwave dielectric ceramic LiBSiO4
CN104446474B (en) The microwave-medium ceramics NdBiWO of temperature coefficient of resonance frequency nearly zero6
CN106082995A (en) High quality factor temperature-stable microwave dielectric ceramic Ba2liB5o10and preparation method thereof
CN106116522A (en) Temperature-stable ultralow dielectric microwave dielectric ceramic Mg3li2b2o7and preparation method thereof
CN105801117A (en) Temperature-stable microwave dielectric ceramic Ba3SmV3O12 capable of being sintered at low temperature and preparation method of microwave dielectric ceramic Ba3SmV3O12
CN105777104A (en) Temperature-stable low-dielectric-constant microwave dielectric ceramic Ba3Bi2Ge3O12 and preparation method thereof
CN105801116A (en) Microwave dielectric ceramic Sr3LaV3O12 with ultralow dielectric constant and preparation method thereof
CN106116525A (en) High quality factor temperature-stable microwave dielectric ceramic LiGaGe3o8
CN106116530A (en) High quality factor temperature-stable microwave dielectric ceramic LiAlGe3o8
CN104446375B (en) Temperature-stable ultralow dielectric microwave dielectric ceramic BaLa0.8nd1.2b10o19
CN104557014B (en) A kind of ultralow dielectric microwave dielectric ceramic of temperature coefficient of resonance frequency nearly zero and preparation method thereof
CN104557020B (en) A kind of sintered at ultra low temperature ultralow dielectric microwave dielectric ceramic and preparation method thereof
CN104355611B (en) Ultralow dielectric microwave dielectric ceramic InAlZn5o8and preparation method thereof
CN104478429B (en) Temperature-stable ultralow dielectric microwave dielectric ceramic Li2znO2and preparation method thereof
CN105859277A (en) High-quality-factor microwave dielectric ceramic Li2Cu3V2O9 which can be sintered at low temperature and preparation method thereof
CN106116523A (en) A kind of germanate LiBGeO4application as temperature-stable microwave dielectric ceramic
CN105801102A (en) Microwave dielectric ceramic Mg3Bi2Ge3O12 with high quality factor and 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
RJ01 Rejection of invention patent application after publication

Application publication date: 20160921

RJ01 Rejection of invention patent application after publication