CN104446374B - Temperature-stable ultralow dielectric microwave dielectric ceramic Ca5laB3o11 - Google Patents

Temperature-stable ultralow dielectric microwave dielectric ceramic Ca5laB3o11 Download PDF

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CN104446374B
CN104446374B CN201410645679.XA CN201410645679A CN104446374B CN 104446374 B CN104446374 B CN 104446374B CN 201410645679 A CN201410645679 A CN 201410645679A CN 104446374 B CN104446374 B CN 104446374B
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dielectric ceramic
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CN104446374A (en
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方维双
唐莹
苏和平
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Shandong Xingqiang Chemical Industry Technology Research Institute Co., Ltd
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Guilin University of Technology
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Abstract

The invention discloses a kind of low temperature sintering temperature-stable ultralow dielectric microwave dielectric ceramic Ca5LaB3O11And preparation method thereof.(1) be 99.9%(percentage by weight by purity) more than CaCO3、La2O3And H3BO3Starting powder press Ca5LaB3O11Composition weigh dispensing;(2) by step (1) raw material wet ball-milling mix 12 hours, ball-milling medium is absolute ethyl alcohol, after drying in 500 DEG C of air atmosphere pre-burning 12 hours;(3) after adding binding agent granulation in the powder that step (2) prepares, re-compacted shaping, finally sinter 10 hours in 870 ~ 910 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.Ceramic post sintering prepared by the present invention is good, and dielectric constant reaches 6.5~6.9, and its quality factor q f value is up to 97000-141000GHz, and temperature coefficient of resonance frequency is little, industrially has great using value.

Description

Temperature-stable ultralow dielectric microwave dielectric ceramic Ca5LaB3O11
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, telstar recipient 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 permittivity 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 endurance, 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.
Three performance indications (ε due to 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, electronic component With material, phase March the 3rd in 2005), the single-phase microwave-medium ceramics meeting three performance requirements is considerably less, is mainly theirs Temperature coefficient of resonance frequency is the most excessive or quality factor are on the low side and cannot application request.At present to microwave-medium ceramics Research major part be the summary of experience drawn by great many of experiments, but there is no complete theory to illustrate microstructure and Jie The relation of electrical property, therefore, the most also cannot predict its temperature coefficient of resonance frequency from the composition of compound with structure With the microwave dielectric properties such as quality factor, explore and develop near-zero resonance frequency temperature coefficient (-10 ppm/DEG C≤τƒ≤+10 Ppm/ DEG C) it is that those skilled in the art thirst for solving always with the serial differing dielectric constant microwave dielectric ceramic of higher figure of merit Determine but be difficult to the difficult problem succeeded all the time, which greatly limits the development of microwave dielectric ceramic and device.
Summary of the invention
It is an object of the invention to provide one and there is good thermal stability and low-loss ultralow dielectric micro-wave dielectric Ceramic material and preparation method thereof.
The chemical composition of the microwave dielectric ceramic material of the present invention is Ca5LaB3O11
The preparation method step of this microwave dielectric ceramic material is:
(1) be 99.9%(percentage by weight by purity) more than CaCO3、La2O3And H3BO3Starting powder press Ca5LaB3O11Composition weigh dispensing.
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is absolute ethyl alcohol, big at 500 DEG C after drying Pre-burning 12 hours in gas atmosphere.
(3), after adding binding agent granulation in the powder that step (2) prepares, re-compacted shaping, finally at 870 ~ 910 DEG C Air atmosphere sinters 10 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.
Advantages of the present invention: Ca5LaB3O11Ceramic sintering temperature is low, and dielectric constant reaches 6.5~6.9, its resonant frequency Temperature coefficient τƒLittle, temperature stability is good;Quality factor q f value is up to 97000-141000GHz, can be widely used for various Jie The manufacture of the microwave devices such as matter substrate, resonator and wave filter, can meet low temperature co-fired technology and the technology of microwave multilayer device Need, industrially have great using value.
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 low temperature sintering temperature-stable ultralow dielectric microwave dielectric ceramic, it is characterised in that described microwave is situated between The chemical composition of electroceramics is: Ca5LaB3O11
The preparation method of described microwave dielectric ceramic concretely comprises the following steps:
(1) be 99.9%(percentage by weight by purity) more than CaCO3、La2O3And H3BO3Starting powder press Ca5LaB3O11's Composition weighs dispensing;
(2) being mixed 12 hours by step (1) raw material wet ball-milling, ball-milling medium is absolute ethyl alcohol, 500 DEG C of pre-burnings 12 after drying Hour;
(3), after adding binding agent granulation in the powder that step (2) prepares, re-compacted shaping, finally at 870 ~ 910 DEG C of air Atmosphere sinters 10 hours;Described binding agent uses mass concentration to be the poly-vinyl alcohol solution of 5%, and polyvinyl alcohol addition accounts for The 3% of powder gross mass.
CN201410645679.XA 2014-11-15 2014-11-15 Temperature-stable ultralow dielectric microwave dielectric ceramic Ca5laB3o11 Active CN104446374B (en)

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Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100427796B1 (en) * 2001-06-25 2004-04-28 주식회사 케이엠더블유 Dielectric ceramic composition and the preparation thereof
US6800577B2 (en) * 2002-03-20 2004-10-05 Council Of Scientific And Industrial Research Microwave dielectric ceramic composition of the formula xmo-yla2o3-ztio2 (m=sr, ca; x:y:z=1:2:4, 2:2:5, 1:2:5 or 1:4:9), method of manufacture thereof and devices comprising the same
CN102417350A (en) * 2011-09-03 2012-04-18 桂林理工大学 Temperature-stable low-cost microwave dielectric ceramic material and preparation method thereof
CN103232243A (en) * 2013-05-14 2013-08-07 桂林理工大学 Vanadate microwave dielectric ceramic Ca1. 5M3V3O12 and preparation method thereof
CN103496972B (en) * 2013-10-01 2015-01-07 桂林理工大学 Ultralow sintering temperature stable type microwave dielectric ceramic Ca5Bi14O26 and preparation method thereof

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