CN105669199B - A kind of microwave-medium ceramics and preparation method thereof - Google Patents
A kind of microwave-medium ceramics and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of microwave-medium ceramics and preparation method thereof.Microwave-medium ceramics include principal crystalline phase, and the chemical expression of principal crystalline phase is Zr0.8Sn0.2‑x(Mg1/3Nb2/3)xTiO4, wherein 0 x≤0.2 ＜.Our experiments show that microwave dielectric ceramic materials provided by the invention have good microwave dielectric property：Permittivity εr=38~42, and be adjusted within this range；Quality factor q *f=60000~70000GHz；Frequency-temperature coefficient τf=2.5~+6.3 × 10‑6/ DEG C within the scope of be adjusted, temperature characterisitic stablize.Microwave-medium ceramics preparation method sintering temperature provided by the invention is relatively low, has saved energy cost, meets low-carbon environment-friendly theory.Preparation process is simple simultaneously, is not necessarily to special installation and stringent process conditions, is suitble to industrialized production.
Description
Technical field
The invention belongs to electronically materials and component fields more particularly to a kind of microwave-medium ceramics and preparation method thereof.
Background technology
Microwave dielectric material is a kind of new function electron ceramic material developed rapidly over the past two decades.It is filter
Critical material in the microwave devices such as wave device, duplexer, resonator and Medium Wave Guide circuit, be widely used in satellite communication,
It is one of the hot spot of current media material in the microwave telecommunication devices such as mobile communication, electronic countermeasure and airborne communication.
Zr0.8Sn0.2TiO4For ceramics as a kind of traditional microwave dielectric material, microwave band is millimere-wave band (wavelength model
It encloses：1~10mm) when, there is medium dielectric constant microwave medium (εr≈ 40), high quality factor q *f, nearly zero temperature coefficient of resonance frequency τf
Equal microwave dielectric properties, but that there are sintering temperatures is high (being higher than 1400 DEG C), and energy consumption is larger in preparation process, does not meet low-carbon environment-friendly
Theory.
As mobile communication technology continues to develop, the miniaturization and high-quality of microwave device are put forward higher requirements, this
It is claimed below to require that microwave-medium ceramics dielectric material should meet：(1) there is suitable medium dielectric constant microwave medium εr；(2) high-quality because
Number Q*f；(3) temperature coefficient τfNearly zero；(4) low-carbon energy-saving.Therefore this field it is necessary to provide a kind of microwave dielectric property preferably and
Lower microwave-medium ceramics of price and preparation method thereof.
Invention content
In view of this, the present invention provides a kind of microwave-medium ceramics, including principal crystalline phase, the chemistry expression of the principal crystalline phase
Formula is Zr0.8Sn0.2-x(Mg1/3Nb2/3)xTiO4, wherein 0 x≤0.2 ＜.
In some embodiments, further include sintering aid, the sintering aid is Li2O、B2O3、Bi2O3In any
One or more combination.
In some embodiments, further include property-modifying additive, the property-modifying additive is MnO2、Co2O3、Ga2O3In
Any or several combination.
In some embodiments, principal crystalline phase molar percentage shared in microwave-medium ceramics be 90~
95mol%.
In some embodiments, sintering aid molar percentage shared in microwave-medium ceramics is 2.0
~5.0mol%.
In some embodiments, property-modifying additive molar percentage shared in microwave-medium ceramics is
1.0~5.0mol%.
The present invention also provides a kind of preparation methods of microwave-medium ceramics, include the following steps：
(1) ZrO is taken according to the stoichiometric ratio of the chemical expression of principal crystalline phase2、SnO2、MgO、Nb2O5、TiO2After carry out
It is dried to obtain the first mixture after ball milling or husky mill；
(2) the first mixture pre-burning is obtained into powder；
(3) powder is added after property-modifying additive and sintering aid and carries out second of ball milling or husky mill, after dry
Obtain the second mixture；
(4) green compact are made after adhesive granulation, compression moulding being added in second mixture；
(5) green compact described in obtain microwave-medium ceramics through sintering.
In some embodiments, in the step (2), the first mixture obtains powder through 800 DEG C~1000 DEG C pre-burnings
Material；In the step (5), green compact obtain microwave-medium ceramics through 1200 DEG C~1300 DEG C sintering.
In some embodiments, in the step (1), first time ball milling or husky time consuming are 8~16 hours.
In some embodiments, in the step (3), second of ball milling or husky time consuming are 8~24 hours.
Compared with prior art, microwave-medium ceramics provided by the invention have the advantage that：
(1) microwave dielectric property is preferable：Permittivity εr=38~42, and be adjusted within this range；Quality factor q *f
=60000~70000GHz；Frequency-temperature coefficient τf=-2.5~+6.3 × 10-6/ DEG C, and be adjusted within this range；Temperature
Stability of characteristics；
(2) in the preparation method of microwave-medium ceramics provided by the invention, sintering temperature is relatively low, has saved energy cost,
Meet the theory of low-carbon environment-friendly；
(3) preparation process of the present invention is simple, is not necessarily to special installation and stringent process conditions, is suitble to industrialized production.
It follows that microwave-medium ceramics provided by the invention are with a wide range of applications.
Description of the drawings
Fig. 1 is Zr0.8Sn0.2-x(Mg1/3Nb2/3)xTiO4The SEM of microwave-medium ceramics schemes.
Specific implementation mode
The claim of the present invention is described in further detail with reference to the mode of specific embodiment, following
Many details are elaborated in description in order to fully understand the present invention.
But the invention can be embodied in many other ways as described herein, those skilled in the art can be with
Similar improvement is done without violating the connotation of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
The present invention provides a kind of microwave-medium ceramics, including principal crystalline phase, the chemical expression of principal crystalline phase is Zr0.8Sn0.2-x
(Mg1/3Nb2/3)xTiO4, wherein (0 x≤0.2 ＜).
Above-mentioned, microwave-medium ceramics are other than belonging to ionic crystal structural polysilicon material, often or composite diphase material, usually
By principal crystalline phase, one or more miscellaneous, compositions such as stomata.
Wherein, Sn4+、(Mg1/3Nb2/3)4+Ionic polarizability and ionic radius it is different, by Zr4+Substitution promotes brilliant
Purpose of the lattice distortion to improve quality factor, adjust dielectric constant, and by adjusting Sn4+Content can make resonant frequency temperature
Spend coefficient τfIt is adjusted to zero.
It is to be appreciated that structure and the simple niobates of component are the Novel microwave dielectric ceramic materials developed in recent years
Material, all niobates are all columbite structures, and τfFor negative value.
Preferably, microwave-medium ceramics further include sintering aid, and the sintering aid is Li2O、B2O3、Bi2O3In appoint
One one or more combination.
It is above-mentioned, realize the low-temperature sintering of microwave-medium ceramics using sintering aid is added, it is relatively inexpensive, effective.Li2O、
B2O3、Bi2O3Belong to lower melting-point oxide, the liquid phase that when sintering generates accelerates the rearrangement of particle or crystal grain, to drop
Low sintering temperature forms active liquid-phase sintering.When active liquid-phase sintering due between particle existing liquid phase to generate
Huge capillary force so that particle occurs sliding and resets, while capillary force caused by liquid phase can also cause solid phase
The dissolving of particle-precipitation process makes smaller grain dissolution, larger particle growth.In grain contact point, larger capillary force
Solid-solution degree is set to increase, substance is just migrated by high-dissolvability area to low solubility area, to keep the particle of contact zone gradually flat
It is smooth and adjacent to each other, so that green body is shunk up to densification, carry out comparatively dense sintering, reduce stomata, reduces sintering temperature
Degree, to carry out low-temp liquid-phase sintering.
Preferably, microwave ceramic dielectric material further includes property-modifying additive MnO2、Co2O3、Ga2O3In it is any or several
Kind combination.
It is above-mentioned, internal structure change and generated corresponding dielectric properties of the ion substitution to microwave ceramic dielectric material
Change difference, by the phase structure to modified principal crystalline phase, microstructure Analysis of Dielectric Properties, it can be found that different ion half
Diameter, polarizability, electronegativity and valence state ion doping be affected to the performance of principal crystalline phase, the experiment proved that MnO2、Co2O3With
Ga2O3All have the dielectric properties for improving microwave ceramic dielectric material, the effect for reducing sintering temperature.
Wherein, above-mentioned microwave-medium ceramics are changed into the electronics of tight-binding by adulterating Mn ions, attraction free electron,
The reduction that can inhibit Ti ions prevents in sintering process due to oxygen deficiency, Ti4+It is reduced to Ti3+, so as to cause dielectric
Loss increases, and the dielectric properties of microwave-medium ceramics deteriorate.
Preferably, total content of the principal crystalline phase in microwave dielectric ceramic materials is 90~95mol%.
Preferably, sintering aid molar percentage shared in microwave dielectric ceramic materials be 2.0~
5.0mol%.
Above-mentioned, the change in dielectric constant of composite diphase material obeys logarithm mixing rule, controls miscellaneous content, especially reduces gas
Hole content makes ceramics sample densified sintering product be particularly important.
When the dosage of sintering aid is excessively high, the liquid phase that ceramics generate in sintering process can be more, promote grain growth
Individual crystalline grains abnormal growth is also resulted in simultaneously, and even grain size is deteriorated, is unfavorable for the raising of density instead, that is, works as liquid phase
Amount is more than that optimum content is also no longer conducive to densification process.
Preferably, property-modifying additive molar percentage shared in microwave dielectric ceramic materials be 1.0~
5.0mol%.
It is above-mentioned, it is to be understood that the mode of doping vario-property additive is divided into two kinds：First, first synthesizing principal crystalline phase chemical combination
Object, then doping vario-property additive；Second is that synthesizing the feed proportioning stage of principal crystalline phase compound with regard to doping vario-property additive.
Preferably, the sintering aid includes Li2O、B2O3、Bi2O3, wherein Li2Molar percentage shared by O is 0.5
~1.5mol%, B2O3Shared molar percentage is 0.5~2mol%, Bi2O3Shared molar percentage be 1~
1.5mol%.
It is above-mentioned, B2O3The effect for reducing sintering temperature is best, but needs to control its ratio in sintering aid, to anti-
The only deterioration of microwave-medium ceramics dielectric properties；Li2O、B2O3、Bi2O3The molar percentage of three should control in proper range
While dielectric loss, temperature when sintered microwave dielectric ceramics is reduced.
Preferably, the property-modifying additive includes MnO2、Co2O3、Ga2O3, wherein MnO2Shared molar percentage is 0
~1mol%, Co2O3Shared molar percentage is 0~1mol%, Ga2O3Shared molar percentage is 1~3mol%.
MnO2、Co2O3、Ga2O3The property-modifying additive that three forms in proper range, microwave-medium ceramics sintering when,
When consistency is reached preferably, it is hardly visible stomata, grain development is more complete, and grain size consistency is preferable.But more than certain
When value, the surface liquid phase of microwave-medium ceramics gradually increases, and grain size consistency is poor, will influence the compactness of ceramics.
The experiment proved that above-mentioned microwave dielectric ceramic materials have low-loss and good microwave dielectric property dielectric constant
ε=38~42, and be adjusted within this range；Quality factor q *f=60000~70000GHz；Frequency-temperature coefficient τf=-2.5
~+6.3 × 10-6/ DEG C within the scope of be adjusted, temperature characterisitic stablize.
The present invention provides a kind of preparation methods of microwave-medium ceramics, include the following steps：
Step (1)：ZrO is taken according to the stoichiometric ratio of the chemical expression of principal crystalline phase2、SnO2、MgO、Nb2O5、TiO2Afterwards
It is dried to obtain the first mixture after carrying out first time ball milling or husky mill；
It is above-mentioned, in step (1), it is preferable that be more than 99% ZrO with purity2、SnO2、MgO、Nb2O5And purity is more than
99.9% TiO2For initial feed；It is put into ball milling in ball mill.The purpose of first time ball milling is to make powder refine and mix
Close equal Uniform.
Preferably, initial feed is put into polyester tank, and deionized water is added, and zirconium ball, the ball on planetary ball mill is added
It grinds several hours, rotating speed is 300~800 revs/min.
It is understood that deionized water can also be alcohol.
Preferably, initial feed, zirconium ball, deionized water (alcohol) volume ratio be 1:5:0.7~1.5.
The planetary-type grinding machine is made of ball grinder, fangs, turntable, fixed pulley and motor etc., on turntable
There are four ball grinders, and when turntable rotates, ball grinder makees planetary motion with turntable around same axle center, that is, central shaft, is ground in tank
Expect that the raw material being submerged is ground and mixed in high-speed motion.This kind of ball grinder rotating speed is fast, and grinding efficiency is high, compact-sized, behaviour
Facilitate, sealing sampling, securely and reliably, noise is low, pollution-free, lossless.
Of course, it should be understood that other ball milling methods and other mixer-mills can also be used.
It is to be understood that using high pure raw material, powder particle size can be reduced, prepares high pure of large specific surface area, activity
Superfines can increase sintering power, promote reactive sintering, to effectively reduce sintering temperature.
Preferably, the initial feed after ball milling is put into drying box, in 100~120 DEG C of drying, then crosses 40 mesh sieve, mistake
Initial feed after sieve is uniformly dispersed, and is convenient for pre-burning.
Step (2)：The first mixture pre-burning is obtained into powder.
Above-mentioned, the purpose of pre-burning and can be largely formed required to allow native oxide to carry out preliminary reaction
Crystallization reduces the contraction distortion of porcelain, the structure of feed change is in favor of being molded and being sintered, to change using principal crystalline phase
It is apt to the dielectric properties of ceramics, to ensure the quality of final products.
When avoiding direct sintering after being molded, ceramic shrinkage rate is big, and ceramics easily deform upon cracking etc..
Step (3)：The powder is added after property-modifying additive and sintering aid and carries out second of ball milling or husky mill, is done
The second mixture is obtained after dry；
Aforementioned, property-modifying additive is mainly to main three parameter dielectric constants, the qualities of microwave-medium ceramics dielectric properties
Factor and temperature coefficient of resonance frequency are improved and are optimized.Microwave-medium ceramics are mainly made of crystalline phase, crystal boundary, stomata etc.,
Belong to the polycrystalline material of ionic structure.The increase of population can improve Jie in the raising of ceramic material density and unit volume
Electric constant.The porosity is reduced, many stomatas can be formed in ceramic body sample sintering process, this, which exactly reduces density of material, causes to be situated between
The one of the major reasons that electric constant declines.
Another kind is that can select different radii size, not homopolarity to the method for the macro adjustments and controls dielectric constant of ceramic material
The ion of rate, by the positions A to its main phase, B progress ion exchanges, to make unit cell volume change with polarizability.
Second phase of ceramic material can similarly influence the variation of dielectric constant, so the production quantity of the second phase of control is also important consideration
One of factor.
It is experimentally verified that Mn4+、Co3+And Ga3+It is sintered temperature with improving the dielectric properties of microwave ceramic dielectric material, reducing
The effect of degree.
Preferably, the powder obtained after pre-burning keeps the temperature 2~8 hours.
Furthermore second of ball milling makes in step (3), and preburning powdered material and property-modifying additive and sintering aid mix Uniform and thin
Change, be likely to that there is also no complete initial feeds of solid phase reversal in the powder after pre-burning, at this moment ball milling again, promotes
Pilot process object or initial feed provide the chance for increasing reaction.
It if without the secondary ball milling process after pre-burning, will lead to that crystal grain is larger and size is uneven, also affect ceramic burning
The grain rearrangement of knot process and densification.
Preferably, the mixture of the powder after ball milling and property-modifying additive and sintering aid is put into drying box, in 100
Then~120 DEG C of drying cross 40 mesh sieve, are uniformly dispersed.
Step (4)：Green compact are made after adhesive granulation, compression moulding is added in second mixture.
Above-mentioned, granulation is a leading technique of compression moulding；Because ceramic powder is comparatively fine, and powder is thinner, table
Face activity is bigger, then the gas of its adsorption is also more, thus its bulk density is also smaller, so to be carried plus adhesive
Blank density after high dry-pressing.It is understood that the amount that adhesive is added should be appropriate, excessively few then difficult forming is crossed at most
The consistency that sample can be reduced influences its performance.
Adhesive can be polyvinyl alcohol (Polyvinyl alcohol, PVA), paraffin or novolaks.It is appreciated that
In practical applications, adhesive may be other kinds of adhesive.
Preferably, adhesive use mass percent for 8%~10% polyvinyl alcohol (Polyvinyl alcohol,
PVA) solution is granulated as adhesive, and 80 mesh sieve is crossed after granulation, green compact are made with the pressure of 4MPa with powder compressing machine,
Green compact a diameter of 10mm, thickness 5mm.
Preferably, adhesive uses mass percent for 8% polyvinyl alcohol (Polyvinyl alcohol, PVA) solution.
Preferably, the second mixture, which is added after adhesive is granulated, crosses 80 mesh sieve.
Preferably, green compact dumping at a certain temperature.
It is understood that it is unsuitable too fast to heat up when dumping, cause in green compact that there are stomatas.
Preferably, by green compact in 600 DEG C of dumping 4h, required temperature when then rising to sintering according to the rate of 3~5 DEG C/min
Degree keeps the temperature several hours.
Step (5)：The green compact obtain microwave-medium ceramics through sintering.
When improving sintering temperature, for the microwave-medium ceramics of 0 x≤0.2 ＜, Q*fValue is all first to increase, and is then started
Decline or saturation.
Preferably, microwave-medium ceramics obtained should be cooled down with sintering furnace after sintering.
In conclusion the preparation method that the present invention provides microwave-medium ceramics includes step (1)~step (5)；Using admittedly
Initial feed is uniformly mixed by phase reaction method according to the method for preset blending ratio physics, and after pre-burning, addition property-modifying additive changes
The crystal structure of principal crystalline phase has been apt to it, while has added consistency when sintering aid improves sintering green compact in crystal, has reduced gas
Hole, to realize the sintering temperature for being sintered to low-temp liquid-phase sintering, reducing in solid reaction process in step (5).The party
Method technique is very ripe, it is simple, of low cost, be convenient for industrialized production, be the prefered method of industrialized production.
Preferably, in the step (2), the first mixture obtains powder through 800 DEG C~1000 DEG C pre-burnings；The step
Suddenly in (5), green compact obtain microwave-medium ceramics through 1200 DEG C~1300 DEG C sintering.
Above-mentioned, calcined temperature is unsuitable excessively high, and calcined temperature is excessively high, and the reunion of preburning powdered material is serious, it is difficult to carry out secondary ball
Mill.Calcined temperature is too low, can influence grain rearrangement and the densification of ceramic post sintering process.
Furthermore sintering temperature should control in a certain range, and sintering temperature is too low, and crystal grain coarsening rate is excessively slow or even nothing
Method is grown up.It obviously grows up as sintering temperature improves crystal grain, grain circle gap is reduced, and grain development is abundant, and apparent porosity reduces.
But when sintering temperature is excessively high, abnormal growth will occur in crystal grain, and apparent porosity increases, under the uniformity of grain growth, consistency
Drop.Meanwhile the probability that excessive crystal grain occurs when the defects of Dislocations, Lacking oxygen increases, and results in Q*fValue is rapid to be declined.
Therefore excessively high and mistake sintering temperature and low can all influence the normal growth of crystal grain.
Preferably, in the step (2), the first mixture obtains powder through 900 DEG C of pre-burnings；In the step (5),
Green compact obtain microwave-medium ceramics through 1260 DEG C of sintering.
Preferably, in the step (2), powder of first mixture through 900 DEG C of pre-burnings keeps the temperature 4 hours.
Preferably, in the step (5), green compact keep the temperature 6 hours after 1260 DEG C of sintering and obtain microwave-medium ceramics.
Preferably, in the step (1), first time ball milling or husky time consuming are 8~16 hours.
Preferably, in the step (1), first time ball milling or husky time consuming are 10 hours, and rotating speed is 400 revs/min.
Preferably, in the step (3), second of ball milling or husky time consuming are 8~24 hours.
Preferably, in the step (3), second of ball milling or husky time consuming are 16 hours, and rotating speed is 400 revs/min.
Hereinafter, being expanded on further by specific embodiment.
Specific embodiment and related process parameters refer to table 1.
Table 1
The test result of the related microwave dielectric property of specific embodiment refers to table 2.
Table 2
| Embodiment | Permittivity εr | Quality factor q *f(GHz) | Temperature coefficient of resonance frequency τf(ppm/℃) |
| 1 | 38.3 | 61235 | -1.5 |
| 2 | 39.8 | 64520 | 3.5 |
| 3 | 40.7 | 66520 | 5.4 |
| 4 | 41.6 | 67525 | 5.5 |
| 5 | 38.6 | 63515 | -2.0 |
| 6 | 40.1 | 65426 | 3.2 |
| 7 | 40.4 | 64585 | 4.8 |
| 8 | 41.8 | 69560 | 6.3 |
| 9 | 38.5 | 62850 | -2.5 |
| 10 | 39.2 | 61256 | 1.8 |
| 11 | 40.6 | 66325 | 5.2 |
| 12 | 41.3 | 67250 | 5.6 |
The microwave-medium ceramics that 1~embodiment of above-described embodiment 12 is prepared have good microwave dielectric property：It is situated between
Electric constant εr=38~42, and be adjusted within this range；Quality factor q *f=60000~70000GHz；Frequency-temperature coefficient
τf=-2.5~+6.3 × 10-6/ DEG C within the scope of be adjusted, temperature characterisitic stablize.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (5)
1. a kind of microwave-medium ceramics, it is characterised in that：Including principal crystalline phase, the chemical expression of the principal crystalline phase is
Zr0.8Sn0.2-x(Mg1/3Nb2/3)xTiO4, wherein 0 x≤0.2 ＜；
Further include sintering aid and property-modifying additive, the sintering aid is Li2O、B2O3、Bi2O3In it is any or several
Kind combination；The property-modifying additive is MnO2、Co2O3、Ga2O3In any or several combination；The principal crystalline phase exists
Shared molar percentage is 90~95mol% in microwave-medium ceramics；Sintering aid institute in microwave-medium ceramics
The molar percentage accounted for is 2.0~5.0mol%；Property-modifying additive Mole percent shared in microwave-medium ceramics
Than for 1.0~5.0mol%.
2. a kind of preparation method of microwave-medium ceramics as described in claim 1, it is characterised in that：
(1) ZrO is taken according to the stoichiometric ratio of the chemical expression of principal crystalline phase2、SnO2、MgO、Nb2O5、TiO2It carries out afterwards for the first time
It is dried to obtain the first mixture after ball milling or husky mill；
(2) the first mixture pre-burning is obtained into powder；
(3) powder is added after property-modifying additive and sintering aid and carries out second of ball milling or husky mill, obtained after dry
Second mixture；
(4) green compact are made after adhesive granulation, compression moulding being added in second mixture；
(5) green compact described in obtain microwave-medium ceramics through sintering.
3. the preparation method of microwave-medium ceramics as claimed in claim 2, it is characterised in that：In the step (2), first
Mixture obtains powder through 800 DEG C~1000 DEG C pre-burnings；In the step (5), green compact are sintered through 1200 DEG C~1300 DEG C
To microwave-medium ceramics.
4. the preparation method of microwave-medium ceramics as claimed in claim 2, it is characterised in that：In the step (1), first
Secondary ball milling or husky time consuming are 8~16 hours.
5. the preparation method of microwave-medium ceramics as claimed in claim 2, it is characterised in that：In the step (3), second
Secondary ball milling or husky time consuming are 8~24 hours.
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