CN106145931B - A kind of ultra-low loss microwave dielectric ceramic materials and preparation method thereof - Google Patents

A kind of ultra-low loss microwave dielectric ceramic materials and preparation method thereof Download PDF

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CN106145931B
CN106145931B CN201610450213.3A CN201610450213A CN106145931B CN 106145931 B CN106145931 B CN 106145931B CN 201610450213 A CN201610450213 A CN 201610450213A CN 106145931 B CN106145931 B CN 106145931B
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ball milling
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dielectric ceramic
microwave dielectric
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唐斌
方梓烜
司峰
钟朝位
张树人
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University of Electronic Science and Technology of China
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Abstract

The invention discloses a kind of ultra-low loss microwave dielectric ceramic materials and preparation method thereof, belong to electronic information function material and device arts.The chemical general formula of ceramic material of the present invention is Li2+a(Mg1‑bXb)3YO6CZ, wherein X Ca2+Or Sr2+, Y Ti4+、Sn4+Or Zr4+, Z MgO, ZnO, CaF2Any of or a combination of, 0.03≤a≤0.15,0.01≤b≤0.04,0≤c≤0.15.The raw material of microwave dielectric ceramic materials of the present invention is according to the chemical general formula dispensing, and by first time ball milling mixing, the pre-burning at 980~1200 DEG C is sintered at 1250~1400 DEG C and is made using second of ball milling mixing；The crystalline phase of its manufactured goods is orderly rock salt structure cubic phase.Microwave dielectric ceramic materials provided by the invention realize larger promotion, relative dielectric constant ε in performancerAdjustable between 8~20, quality factor q × f values are 92000GHz~153000GHz, meanwhile, temperature coefficient of resonance frequency τf- 23ppm/ DEG C~+5ppm/ DEG C of satisfaction, and performance is stablized, and disclosure satisfy that the application demand of modern microwave device.

Description

A kind of ultra-low loss microwave dielectric ceramic materials and preparation method thereof
Technical field
The invention belongs to electronic information function material and device arts, and in particular to be a kind of there is frequency temperature Coefficient level off to zero ultra-low loss microwave dielectric ceramic materials.
Background technology
Currently, information technology is just fast-developing towards high frequency, high-power, integrated, multifunction direction, and with the modern times The fast development of mobile communication technology and technology of Internet of things, high-frequency microwave technology is in communication, navigation, satellite, bluetooth, sensing Internet of Things In the systems such as net radio-frequency technique, there is extensive and important application.In high-frequency microwave circuit, many microwave devices need to use Medium ceramic material is as substrate so that microwave ceramics medium baseplate material more and more becomes microwave device, component and complete machine system The key basic material used in system.Using ceramic substrate material high-frequency microwave device usually have miniaturization, wideband, The features such as high reliability.State Council was early in 2009《Planning outline is revitalized in electronics and information industry adjustment》File propose develop be situated between The importance of the excellent media ceramic of electric constant seriation, microwave dielectric property.High-k, high quality factor, frequency temperature Degree coefficient close to zero and sintering temperature it is low be microwave-medium ceramics primary study developing direction.This three performance indicators are micro- The important parameter of wave dielectric material, since the square root of the dielectric constant of the size and dielectric substance of resonator is inversely proportional, therefore High dielectric constant is advantageously implemented the miniaturization of component, since quality factor q × f values of microwave dielectric ceramic materials are got over Greatly, the insertion loss of filter is lower, therefore high quality factor is advantageously implemented the good frequency-selecting of microwave device, and close to zero Frequency-temperature coefficient τfMean that the centre frequency of device is small with variation of ambient temperature, job stability is high.Therefore, it develops There are tunable dielectric constant, the microwave-medium ceramics of ultra-low loss and the frequency-temperature coefficient close to zero simultaneously under microwave frequency Material has prodigious application value.
In order to meet above-mentioned target, a series of high performance binary or ternary Li base microwave ceramics systems are developed in succession Come, such as Li2O-MgO-XO2(X=Ti, Sn, Zr), Li2O-XO2(X=Ti, Zr, Sn), Li2O-Nb2O5, Li2O-MoO3, Li2O-XO-TiO2(X=Mg, Zn, Ca, Co), Li2O-ZnO-Nb2O5Deng.Wherein,《European ceramics association proceedings》(Journal Of the European Ceramic Society) in articles in 2016《The Li of novel super-low loss2Mg3BO6(B=Ti, Sn, Zr) microwave ceramics》(Novel series of ultra-low loss microwave dielectric ceramics: Li2Mg3BO6(B=Ti, Sn, Zr)) in report Li for the first time2Mg3BO6It is the microwave property of microwave ceramics.Wherein, Li2Mg3TiO6：εr=15.2, Q × f=152000GHz, τf=-39ppm/ DEG C；Li2Mg3SnO6：εr=8.8, Q × f= 123000GHz, τf=-32ppm/ DEG C；Li2Mg3TiO6：εr=12.6, Q × f=86000GHz, τf=-36ppm/ DEG C, this is micro- Wave ceramics cause the attention of vast researcher with the quality factor of its superelevation.
Although Li2Mg3BO6Being microwave ceramics has extremely low loss, but has as most of raw microwave ceramics altogether Logical defect.First, under 1280 DEG C~1380 DEG C of high temperature sintering environment, Li+The serious volatilization of ion leads to Li2Mg3SnO6 And Li2Mg3ZrO6In be respectively present the second phase Mg2SnO4(εr=8.3, Q × f=55000GHz, τf=-61ppm/ DEG C) and second Phase ZrO2, the presence of the second phase can make Li2Mg3SnO6And Li2Mg3ZrO6The microwave property severe exacerbation of base-material, and there are materials The phase constituent of material system complicates problem not easy to control；Second, larger negative frequency temperature coefficient makes Li2Mg3BO6It is microwave Ceramics cannot be satisfied practical application request.Dephasign is inhibited to be adulterated frequently with volatilization non-stoichiometric or base-material inside to realize, Such as Li et al., people exists《Co2O3Doping is to 0.95MgTiO3-0.05CaTiO3The influence of the structure and microwave property of ceramics》(The structure and properties of 0.95MgTiO3-0.04CaTiO3ceramics doped with Co2O3) one Successfully utilize Co ions that dephasign, Bian et al. is inhibited to exist in text《Li2+xTiO3The sintering character of (0≤x≤0.2), microstructure And microwave dielectric property》(Sintering behavior,microstructure and microwave dielectric properties of Li2+xTiO3(0≤x≤0.2)) successfully utilize in a text non-stoichiometric of Li elements to realize Li2+ xTiO3The significantly promotion of the comprehensive microwave property of ceramics.At present adjust the most effective method of frequency-temperature coefficient be introduce with The opposite phase of binder systems for use frequency-temperature coefficient is such as introduced in negative frequency temperature coefficient system as MgO (τf=+103ppm/ DEG C) And CaF2(τf=+252ppm/ DEG C) etc. the very big and easily controllable phase of positive frequencys temperature coefficient.
In conclusion with Li2O-MgO-XO2(X=Ti, Sn, Zr) is integrated use based on low damage microwave ceramic material Non-stoichiometric, ionic compartmentation and the method that dopant is added, study a kind of ultra high quality factor (ultra-low loss), close to Zero frequency-temperature coefficient, while the microwave-medium ceramics of dielectric properties can be adjusted in a certain range with before good application Scape can meet microwave communication industry requirement.
Invention content
The object of the present invention is to provide one kind having high quality factor, adjustable dielectric constant, temperature coefficient of resonance frequency Nearly zero adjustable microwave dielectric ceramic materials.It includes Li to specifically provide a kind of form2O-MgO-XO2(X=Ti, Sn, Zr) system Ceramics and dopant, microwave dielectric ceramic materials and its preparation made of ball milling mixing, granulation, molding, dumping and sintering Method, Q × f values are between 92000GHz~153000GHz, relative dielectric constant εrBetween 8~20, resonant frequency temperature Coefficient is between -23ppm/ DEG C~+5ppm/ DEG C；The microwave dielectric ceramic materials preparation process of the present invention is simple, is easy to industrialize Production.
The present invention adopts the following technical scheme that：
A kind of ultra-low loss microwave dielectric ceramic materials, chemical general formula Li2+a(Mg1-bXb)3YO6CZ, wherein X is Ca2+Or Sr2+, Y Ti4+、Sn4+Or Zr4+, Z MgO, ZnO, CaF2Any of or a combination of, 0.03≤a≤0.15, 0.01≤b, 0.04,0≤c≤0.15；
The raw material of the microwave dielectric ceramic materials may include Mg (OH)2·4MgCO3·5H2O, Li2CO3, calcium or strontium Carbonate, titanium, tin or zirconium dioxide, the modifying dopant of specific components can also be increased on its basis, i.e., microwave is situated between The raw material of ceramics can also be following forms：Mg(OH)2·4MgCO3·5H2O, Li2CO3, the carbonate of calcium or strontium, Titanium, the dioxide of tin or zirconium and more than one MgO, ZnO, CaF2；Microwave ceramic material each component is logical by the chemistry Formula dispensing, by first time ball milling mixing, the pre-burning at 980~1200 DEG C, using second of ball milling mixing, 1250~ Sintering is made at 1400 DEG C；The crystalline phase of its manufactured goods is orderly rock salt structure cubic phase；Its Q × f value be 92000GHz~ 153000GHz, temperature coefficient of resonance frequency τfBetween -23ppm/ DEG C~+5ppm/ DEG C, relative dielectric constant εr8~20 it Between it is adjustable.
A kind of preparation method of ultra-low loss microwave dielectric ceramic materials, includes the following steps：
Step 1：Dispensing；By Mg (OH)2·4MgCO3·5H2O, Li2CO3, the carbonate of calcium or strontium, titanium, tin or zirconium two Oxide is according to chemical general formula Li2+a(Mg1-bXb)3YO6, wherein X Ca2+Or Sr2+, Y Ti4+、Sn4+Or Zr4+, 0.03≤a ≤ 0.15,0.01≤b≤0.04 dispensing form mixture；
Step 2：Ball milling；Ball milling material is obtained after step 1 gained mixture is carried out first time ball milling, it is preferable that specific ball Honed journey is：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is 1: (5~7): (2~4) It is ground 5~7 hours, obtains uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in alumina crucible, 980~1200 DEG C of temperature conditions Under, pre-burning obtains pre-burning powder in 3~5 hours；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, it is preferable that specifically mechanical milling process is：Using zirconia balls as ball-milling medium, according to Mixture：Abrading-ball：The mass ratio of ethyl alcohol is 1: (3~5): (1~2) is ground 2~4 hours, obtains uniformly mixed ball milling Material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Granulating agent is added in the dry powder obtained by step 6, is granulated size Control 80 Pellet is put into molding die and green compact is made by~100 mesh；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible, control heating rate be 4~6 DEG C/ Min under 1250~1400 DEG C of temperature conditions, is sintered 4~6 hours, final microwave dielectric ceramic materials is made.
It is Li that the present invention, which can use any suitable feedstock to form chemical general formula,2+a(Mg1-bXb)3YO6CZ, microwave be situated between Ceramics, wherein X Ca2+Or Sr2+, Y Ti4+、Sn4+Or Zr4+, Z MgO, ZnO, CaF2Any one of or its group It closes, 0.03≤a≤0.15,0.01≤b≤0.04,0≤c≤0.15；The present invention is by using Li element non-stoichiometrics, Mg Position ionic compartmentation is that positive dopant is modified with temperature coefficient of resonance frequency is introduced, to reach comprehensive improvement microwave dielectric property Purpose, the present invention, to control Li element evaporations, A bits plain (X) are controlled by adjusting the value of b especially by the value for adjusting a Content, by adjusting the value of c to control the content of dopant Z, to ensure the qualities of prepared microwave dielectric ceramic materials because For number in the case of 92000GHz≤Q × f≤153000GHz, frequency-temperature coefficient is -23ppm/ DEG C≤τf≤+5ppm/℃ And there is the adjustable property of dielectric constant.
Compared with prior art, the invention has the advantages that：
1, microwave dielectric ceramic materials provided by the invention realize larger promotion in performance, prepared by the prior art Microwave dielectric ceramic materials, relative dielectric constant εrBetween 7~16, Q × f values between 86000~152000GHz, but Its temperature coefficient of resonance frequency is much smaller than -32ppm/ DEG C；In contrast, microwave dielectric ceramic materials provided by the invention is opposite Permittivity εrAdjustable between 8~20, Q × f values are 92000GHz~153000GHz, temperature coefficient of resonance frequency τfMeet- 23ppm/ DEG C~+5ppm/ DEG C, and performance is stablized, and disclosure satisfy that the application demand of modern microwave device.
2, Pb is free of in microwave dielectric ceramic materials of the invention, the volatility toxic metals such as Cd can be widely applied to defend It is applied in the microwave devices such as star communications intermediary matter resonator, filter, oscillator, green pollution-free meets the European Community most Newly put into effect RHOS (《Electrically, limitation uses certain Hazardous Substances Directives in electronic equipment》) and recovery processing management rules (WEEE) strict standard requirement.
3, the dopant in microwave dielectric ceramic materials of the invention is simple oxide and fluoride, does not need volume Outer technique synthesis, the nominal frequencies temperature coefficient dopant such as CaTiO separately synthesized better than needs3Deng；The present invention uses two Secondary ball-milling technology realizes the size controlling of material, meanwhile, dopant is introduced in second of ball-milling technology, technique will not be increased Complexity.
4, the raw material of the invention for preparing microwave dielectric ceramic materials is in liberal supply at home, and relative low price makes high property Energy the cost effective of microwave ceramics is possibly realized, therefore has essential industry application value；And microwave-medium ceramics of the present invention The sintering temperature of material is each about 1250~1400 DEG C, and sintering range is wider, has good process adaptability.
Description of the drawings
Fig. 1 is the XRD spectrum of microwave ceramic dielectric material prepared by the embodiment of the present invention 3.
Fig. 2 is microwave ceramic dielectric material scanning electron microscope sem figure prepared by the embodiment of the present invention 3.
Fig. 3 is microwave ceramic dielectric material profile scanning Electronic Speculum SEM figures prepared by the embodiment of the present invention 3.
Specific implementation mode
A kind of ultra-low loss microwave dielectric ceramic materials, chemical general formula Li2+a(Mg1-bXb)3YO6CZ, wherein X is Ca2+Or Sr2+, Y Ti4+、Sn4+Or Zr4+, Z MgO, ZnO, CaF2Any of or a combination of, 0.03≤a≤0.15, 0.01≤b≤0.04,0≤c≤0.15.
The raw material of the microwave dielectric ceramic materials may include Mg (OH)2·4MgCO3·5H2O, Li2CO3, calcium or strontium Carbonate, titanium, tin or zirconium dioxide, the modifying dopant of specific components can also be increased on its basis, i.e., microwave is situated between The raw material of ceramics can also be following forms：Mg(OH)2·4MgCO3·5H2O, Li2CO3, the carbonate of calcium or strontium, Titanium, the dioxide of tin or zirconium and more than one MgO, ZnO, CaF2；Microwave ceramic material each component is logical by the chemistry Formula dispensing, by first time ball milling mixing, the pre-burning at 980~1200 DEG C, using second of ball milling mixing, 1250~ Sintering is made at 1400 DEG C；The crystalline phase of its manufactured goods is orderly rock salt structure cubic phase；Its Q × f value be 92000GHz~ 153000GHz, temperature coefficient of resonance frequency τfBetween -23ppm/ DEG C~+5ppm/ DEG C, relative dielectric constant εr8~20 it Between.
Below in conjunction with specific embodiment, invention is further explained, and table 1 is that chemical general formula of the present invention is Li2+a (Mg1-bXb)3YO6The each component mass percentage data form of the specific embodiment of the microwave dielectric ceramic materials of cZ, In, X Ca2+Or Sr2+, Y Ti4+、Sn4+Or Zr4+, Z MgO, ZnO, CaF2Any of or a combination of, 0.03≤a≤ 0.15,0.01≤b≤0.04,0≤c≤0.15；
Table 1
Embodiment 1：
Step 1：Dispensing；According to Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate) 62.64%, Li2CO316.79%, TiO217.88% and CaCO32.69% mass percent dispensing obtains mixture；
Step 2：Ball milling；Ball milling material, specific mechanical milling process are obtained after step 1 gained mixture is carried out first time ball milling For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is ground 7 hours for 1: 5: 3, is obtained To uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, specific mechanical milling process is：Using zirconia balls as ball-milling medium, according to mixture： Abrading-ball：The mass ratio of ethyl alcohol is 1:4:2 are ground 2 hours, obtain uniformly mixed ball milling material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Poly-vinyl alcohol solution is added in the dry powder obtained by step 6 to be granulated, is granulated ruler Very little control is put into molding die in 90 mesh, by pellet and green compact is made；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, are burnt under 1295 DEG C of temperature condition Final microwave dielectric ceramic materials are made in 6 hours in knot.
Embodiment 2：
Step 1：Dispensing；According to Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate) 63.56%, Li2CO316.69%, TiO217.78% and SrCO31.97% mass percent dispensing obtains mixture；
Step 2：Ball milling；Ball milling material, specific mechanical milling process are obtained after step 1 gained mixture is carried out first time ball milling For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is ground 7 hours for 1: 6: 3, is obtained To uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, specific mechanical milling process is：Using zirconia balls as ball-milling medium, according to mixture： Abrading-ball：The mass ratio of ethyl alcohol is 1:3:2 are ground 2 hours, obtain uniformly mixed ball milling material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Poly-vinyl alcohol solution is added in the dry powder obtained by step 6 to be granulated, is granulated ruler Very little control is put into molding die in 90 mesh, by pellet and green compact is made；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, are burnt under 1270 DEG C of temperature condition Final microwave dielectric ceramic materials are made in 6 hours in knot.
Embodiment 3：
Step 1：Dispensing；According to Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate) 62.51%, Li2CO316.24%, TiO2The mass percent dispensing of 17.30% and MgO3.00% obtains mixture；
Step 2：Ball milling；Ball milling material, specific mechanical milling process are obtained after step 1 gained mixture is carried out first time ball milling For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is ground 7 hours for 1: 6: 2, is obtained To uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, specific mechanical milling process is：Using zirconia balls as ball-milling medium, according to mixture： Abrading-ball：The mass ratio of ethyl alcohol is 1:5:1 is ground 2 hours, obtains uniformly mixed ball milling material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Poly-vinyl alcohol solution is added in the dry powder obtained by step 6 to be granulated, is granulated ruler Very little control is put into molding die in 90 mesh, by pellet and green compact is made；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, are burnt under 1260 DEG C of temperature condition Final microwave dielectric ceramic materials are made in 5.5 hours in knot.
Embodiment 4：
Step 1：Dispensing；According to Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate) 55.51%, Li2CO314.92%, SnO228.99% and CaCO30.58% mass percent dispensing obtains mixture；
Step 2：Ball milling；Ball milling material, specific mechanical milling process are obtained after step 1 gained mixture is carried out first time ball milling For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is ground 6 hours for 1: 5: 3, is obtained To uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, specific mechanical milling process is：Using zirconia balls as ball-milling medium, according to mixture： Abrading-ball：The mass ratio of ethyl alcohol is 1:4:2 are ground 3 hours, obtain uniformly mixed ball milling material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Poly-vinyl alcohol solution is added in the dry powder obtained by step 6 to be granulated, is granulated ruler Very little control is put into molding die in 90 mesh, by pellet and green compact is made；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, are burnt under 1360 DEG C of temperature condition Final microwave dielectric ceramic materials are made in 5 hours in knot.
Embodiment 5：
Step 1：Dispensing；According to Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate) 49.96%, Li2CO313.43%, SnO226.09% and CaCO30.52% mass percent dispensing obtains mixture；
Step 2：Ball milling；Ball milling material, specific mechanical milling process are obtained after step 1 gained mixture is carried out first time ball milling For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is ground 6 hours for 1: 5: 3, is obtained To uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, specific mechanical milling process is：Using zirconia balls as ball-milling medium, according to mixture： Abrading-ball：The mass ratio of ethyl alcohol is 1:4:2 are ground 3 hours, obtain uniformly mixed ball milling material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Poly-vinyl alcohol solution is added in the dry powder obtained by step 6 to be granulated, is granulated ruler Very little control is put into molding die in 90 mesh, by pellet and green compact is made；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, are burnt under 1240 DEG C of temperature condition Final microwave dielectric ceramic materials are made in 5 hours in knot.
Embodiment 6：
Step 1：Dispensing；According to Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate) 54.64%, Li2CO314.84%, SnO228.82% and SrCO31.69% mass percent dispensing obtains mixture；
Step 2：Ball milling；Ball milling material, specific mechanical milling process are obtained after step 1 gained mixture is carried out first time ball milling For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is ground 6 hours for 1: 5: 3, is obtained To uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, specific mechanical milling process is：Using zirconia balls as ball-milling medium, according to mixture： Abrading-ball：The mass ratio of ethyl alcohol is 1:4:2 are ground 3 hours, obtain uniformly mixed ball milling material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Poly-vinyl alcohol solution is added in the dry powder obtained by step 6 to be granulated, is granulated ruler Very little control is put into molding die in 90 mesh, by pellet and green compact is made；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, are burnt under 1360 DEG C of temperature condition Final microwave dielectric ceramic materials are made in 6 hours in knot.
Embodiment 7：
Step 1：Dispensing；According to Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate) 46.44%, Li2CO312.61%, SnO2The mass percent dispensing of 24.50% and MgO15.0% obtains mixture；
Step 2：Ball milling；Ball milling material, specific mechanical milling process are obtained after step 1 gained mixture is carried out first time ball milling For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is ground 6 hours for 1: 5: 3, is obtained To uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, specific mechanical milling process is：Using zirconia balls as ball-milling medium, according to mixture： Abrading-ball：The mass ratio of ethyl alcohol is 1:4:2 are ground 3 hours, obtain uniformly mixed ball milling material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Poly-vinyl alcohol solution is added in the dry powder obtained by step 6 to be granulated, is granulated ruler Very little control is put into molding die in 90 mesh, by pellet and green compact is made；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, are burnt under 1320 DEG C of temperature condition Final microwave dielectric ceramic materials are made in 5 hours in knot.
Embodiment 8：
Step 1：Dispensing；According to Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate) 58.09%, Li2CO316.07%, ZrO224.93% and CaCO30.91% mass percent dispensing obtains mixture；
Step 2：Ball milling；Ball milling material, specific mechanical milling process are obtained after step 1 gained mixture is carried out first time ball milling For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is ground 5 hours for 1: 5: 3, is obtained To uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, specific mechanical milling process is：Using zirconia balls as ball-milling medium, according to mixture： Abrading-ball：The mass ratio of ethyl alcohol is 1:4:2 are ground 4 hours, obtain uniformly mixed ball milling material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Poly-vinyl alcohol solution is added in the dry powder obtained by step 6 to be granulated, is granulated ruler Very little control is put into molding die in 90 mesh, by pellet and green compact is made；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, are burnt under 1380 DEG C of temperature condition Final microwave dielectric ceramic materials are made in 6 hours in knot.
Embodiment 9：
Step 1：Dispensing；According to Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate) 51.70%, Li2CO314.30%, ZrO222.19%, CaCO3The mass percent dispensing of 0.81% and ZnO11.0% obtains mixture；
Step 2：Ball milling；Ball milling material, specific mechanical milling process are obtained after step 1 gained mixture is carried out first time ball milling For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is ground 5 hours for 1: 5: 3, is obtained To uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, specific mechanical milling process is：Using zirconia balls as ball-milling medium, according to mixture： Abrading-ball：The mass ratio of ethyl alcohol is 1:4:2 are ground 4 hours, obtain uniformly mixed ball milling material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Poly-vinyl alcohol solution is added in the dry powder obtained by step 6 to be granulated, is granulated ruler Very little control is put into molding die in 90 mesh, by pellet and green compact is made；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, are burnt under 1400 DEG C of temperature condition Final microwave dielectric ceramic materials are made in 6 hours in knot.
Embodiment 10：
Step 1：Dispensing；According to Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate) 57.46%, Li2CO315.98%, ZrO224.79% and SrCO31.78% mass percent dispensing obtains mixture；
Step 2：Ball milling；Ball milling material, specific mechanical milling process are obtained after step 1 gained mixture is carried out first time ball milling For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is ground 5 hours for 1: 5: 3, is obtained To uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, specific mechanical milling process is：Using zirconia balls as ball-milling medium, according to mixture： Abrading-ball：The mass ratio of ethyl alcohol is 1:4:2 are ground 4 hours, obtain uniformly mixed ball milling material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Poly-vinyl alcohol solution is added in the dry powder obtained by step 6 to be granulated, is granulated ruler Very little control is put into molding die in 90 mesh, by pellet and green compact is made；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, are burnt under 1260 DEG C of temperature condition Final microwave dielectric ceramic materials are made in 6 hours in knot.
Embodiment 11：
Step 1：Dispensing；According to Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate) 51.71%, Li2CO314.38%, ZrO222.31%SrCO3The mass percent dispensing of 1.68% and ZnO10% obtains mixture；
Step 2：Ball milling；Ball milling material, specific mechanical milling process are obtained after step 1 gained mixture is carried out first time ball milling For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is ground 5 hours for 1: 5: 3, is obtained To uniformly mixed ball milling material；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；After step 4 gained pre-burning powder is carried out ball milling or dopant is added in the pre-burning powder Ball milling material is obtained after carrying out second of ball milling, specific mechanical milling process is：Using zirconia balls as ball-milling medium, according to mixture： Abrading-ball：The mass ratio of ethyl alcohol is 1:4:2 are ground 4 hours, obtain uniformly mixed ball milling material；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Poly-vinyl alcohol solution is added in the dry powder obtained by step 6 to be granulated, is granulated ruler Very little control is put into molding die in 90 mesh, by pellet and green compact is made；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, are burnt under 1380 DEG C of temperature condition Final microwave dielectric ceramic materials are made in 5 hours in knot.
As shown in table 2 for the microwave dielectric ceramic materials prepared of embodiment cited by the present invention after testing after performance ginseng Number：
Table 2
From table 2 it can be seen that the microwave dielectric ceramic materials that the present invention prepares have the quality factor of superelevation, Q × f values For 92000GHz~153000GHz, temperature coefficient of resonance frequency τfIt it is -23ppm/ DEG C~+5ppm/ DEG C, and relative dielectric constant εr Adjustable, value is between 8~20.
Below by way of Figure of description, invention is further explained：
Fig. 1 is the XRD analysis of microwave ceramic dielectric material prepared by the embodiment of the present invention 3 as a result, as can be seen from Figure 1： The crystalline phase for the microwave dielectric ceramic materials that the present invention prepares is orderly rock salt structure cubic phase.
Fig. 2 is microwave ceramic dielectric material scanning electron microscope sem figure prepared by the embodiment of the present invention 3, is prepared as can be seen from Figure 2 The microwave ceramic material surface grain size gone out is evenly distributed, and CRYSTALLITE SIZES distribution is regular, there is a small amount of stomata；And a small amount of stomata Formation be because the Li elements of ceramic surface can volatilize and leave hole at high temperature.
Fig. 3 is the profile scanning Electronic Speculum SEM figure of microwave ceramic dielectric material prepared by the embodiment of the present invention 3, can be with from Fig. 3 Find out that ceramic internal structure is fine and close.
Above-described embodiment only illustrates that the principle of the present invention and its effect, those skilled in the art can be disclosed by this specification Content recognize advantages of the present invention and effect.Above example, which illustrates rather than, to be further limited, people in the art Member completely can according to be combined into the technical proposal scope that invention content is summarized it is more, the technology of the present invention effect can be reached The specific implementation mode of fruit.Therefore, any person skilled in the art is thinking without departing from disclosed spirit with technology Think lower all completed equivalent modifications or change, should be covered by the claim of the present invention.

Claims (8)

1. a kind of ultra-low loss microwave dielectric ceramic materials, which is characterized in that the chemical general formula of the microwave dielectric ceramic materials For Li2+a(Mg1-bXb)3YO6CZ, wherein X Ca2+Or Sr2+, Y Ti4+、Sn4+Or Zr4+, Z MgO, ZnO, CaF2In appoint One kind or combinations thereof, 0.03≤a≤0.15,0.01≤b≤0.04,0≤c≤0.15；The crystalline substance of the microwave dielectric ceramic materials It is mutually orderly rock salt structure cubic phase.
2. a kind of ultra-low loss microwave dielectric ceramic materials according to claim 1, which is characterized in that the microwave-medium The raw material of ceramic material includes Mg (OH)2·4MgCO3·5H2O, Li2CO3, the carbonate of calcium or strontium, titanium, tin or zirconium titanium dioxide Object, each component presses the chemical general formula dispensing of the microwave dielectric ceramic materials, by first time ball milling mixing, 980~1200 Pre-burning at DEG C is sintered at 1250~1400 DEG C and is made using second of ball milling mixing.
3. a kind of ultra-low loss microwave dielectric ceramic materials according to claim 1, which is characterized in that the microwave-medium The raw material of ceramic material includes Mg (OH)2·4MgCO3·5H2O, Li2CO3, the carbonate of calcium or strontium, titanium, tin or zirconium titanium dioxide The MgO of object and more than one, ZnO, CaF2, each component presses the chemical general formula dispensing of the microwave dielectric ceramic materials, by the Ball milling mixing, the pre-burning at 980~1200 DEG C are sintered system using second of ball milling mixing at 1250~1400 DEG C At.
4. a kind of ultra-low loss microwave dielectric ceramic materials according to claim 2 or 3, which is characterized in that the microwave Q × f values of medium ceramic material are 92000GHz~153000GHz, temperature coefficient of resonance frequency τf- 23ppm/ DEG C~+ Between 5ppm/ DEG C, relative dielectric constant εrBetween 8~20.
5. a kind of preparation method of ultra-low loss microwave dielectric ceramic materials, which is characterized in that include the following steps：
Step 1：Dispensing；By Mg (OH)2·4MgCO3·5H2O, Li2CO3, the carbonate of calcium or strontium, titanium, tin or zirconium titanium dioxide Object is according to chemical general formula Li2+a(Mg1-bXb)3YO6, wherein X Ca2+Or Sr2+, Y Ti4+、Sn4+Or Zr4+, 0.03≤a≤ The dispensings of 0.15,0.01≤b≤0.04 form mixture；
Step 2：Ball milling；Ball milling material is obtained after step 1 gained mixture is carried out first time ball milling；
Step 3：Drying, sieving；It sieves with 100 mesh sieve to obtain dry powder after step 2 gained ball milling material is dried；
Step 4：Pre-burning；The drying powder that step 3 obtains is placed in pre-burning in alumina crucible and obtains pre-burning powder；
Step 5：Ball milling；Step 4 gained pre-burning powder is subjected to ball milling or is carried out after dopant is added in the pre-burning powder Ball milling material is obtained after second of ball milling；The dopant is MgO, ZnO, CaF2Any of or a combination of, quality accounts for institute State pre-burning powder and the dopant mixing after gross mass percentage be not higher than 15%；
Step 6：Drying, sieving；It will sieve with 100 mesh sieve to obtain dry powder after the ball milling material drying obtained by step 5；
Step 7：It is granulated, compression molding；Granulating agent is added in the dry powder obtained by step 6, is granulated size Control 80~100 Pellet is put into molding die and green compact is made by mesh；
Step 8：Sintering；The green compact that step 7 obtains are placed in alumina crucible and are sintered, when sintering heating rate be 4~6 DEG C/ Final microwave dielectric ceramic materials are made in min.
6. a kind of preparation method of ultra-low loss microwave dielectric ceramic materials according to claim 5, which is characterized in that institute Stating specific mechanical milling process in step 2 is：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is 1:(5~7):(2~4) are ground 5~7 hours, obtain uniformly mixed ball milling material；Specific mechanical milling process in the step 5 For：Using zirconia balls as ball-milling medium, according to mixture：Abrading-ball：The mass ratio of ethyl alcohol is 1:(3~5):(1~2) is ground Mill 2~4 hours, obtains uniformly mixed ball milling material.
7. a kind of preparation method of ultra-low loss microwave dielectric ceramic materials according to claim 5, which is characterized in that institute It is 980~1200 DEG C to state calcined temperature in step 4, burn-in time 3~5 hours.
8. a kind of preparation method of ultra-low loss microwave dielectric ceramic materials according to claim 5, which is characterized in that institute It is 1250~1400 DEG C to state sintering temperature in step 8, and sintering time is 4~6 hours.
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CN105503202A (en) * 2016-01-17 2016-04-20 济南大学 Novel low-loss Li2MgZrO4 microwave dielectric ceramic material and preparing method

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