CN105777116A - Microwave dielectric ceramic and preparation method thereof - Google Patents
Microwave dielectric ceramic and preparation method thereof Download PDFInfo
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- CN105777116A CN105777116A CN201610226988.2A CN201610226988A CN105777116A CN 105777116 A CN105777116 A CN 105777116A CN 201610226988 A CN201610226988 A CN 201610226988A CN 105777116 A CN105777116 A CN 105777116A
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Abstract
The invention provides a microwave dielectric ceramic and a preparation method thereof.The microwave dielectric ceramic includes a main crystal phase, a chemical expression formula of the main crystal phase is (1-x) Zr0.5Sn0.5TiO4-x(Ni1/3Ta2/3)TiO, wherein x is greater than or equal to 0.1 but is smaller than or equal to 0.3.Experimental results show that the microwave dielectric ceramic material has good microwave dielectric properties: dielectric constant epsilon r is 40-44 and is adjustable within the range, quality factor Q * f is 45000 to 60000 GHz, frequency temperature coefficient tau f is -8.5 to +15.3 * 10-6/DEG C and is adjustable in the range, and temperature characteristics are stable.The preparation method of the microwave dielectric ceramic is lower in sintering temperature, saves energy costs and conforms to a low-carbon environmental-protection concept.In addition, the preparation process is simple, does not need special equipment and strict process conditions and is suitable for industrial production.
Description
Technical field
The invention belongs to electronically materials and component field, particularly relate to a kind of microwave-medium
Pottery and preparation method thereof.
Background technology
Microwave dielectric material is a kind of new function electricity developed rapidly over the past two decades
Sub-ceramic material.It is that wave filter, duplexer, resonator and Medium Wave Guide loop etc. are micro-
Critical material in wave device, is widely used in satellite communication, mobile communication, electronics
In antagonism and the microwave telecommunication devices such as airborne communication, it it is one of the focus of current media material.
Zr0.8Sn0.2TiO4Pottery is as a kind of traditional microwave dielectric material, and microwave band is
During millimere-wave band (wave-length coverage: 1～10mm), there is medium dielectric constant microwave medium (εr≈40)、
High quality factor q *f, the temperature coefficient of resonance frequency τ of nearly zerofDeng microwave dielectric property,
But it is high (higher than 1400 DEG C) to there is sintering temperature, in preparation process, energy consumption is relatively big, does not meets
The theory of low-carbon environment-friendly.
Along with mobile communication technology development, miniaturization and the high-quality to microwave device
Proposing higher requirement, this just requires that microwave-medium ceramics dielectric material should meet following wanting
Ask: (1) has suitable medium dielectric constant microwave medium εr；(2) high quality factor Q*f；(3) temperature
Degree coefficient τfNearly zero；(4) low-carbon energy-saving.Therefore this area is necessary to provide a kind of microwave
Microwave-medium ceramics that dielectric properties are preferable and price is relatively low and preparation method thereof.
Summary of the invention
In view of this, the invention provides a kind of microwave-medium ceramics, including principal crystalline phase,
The chemical expression of described principal crystalline phase is (1-x) Zr0.5Sn0.5TiO4-x(Ni1/3Ta2/3) TiO,
Wherein (0.1≤x≤0.3).
In some embodiments, property-modifying additive, described property-modifying additive are also included
For MnO2、CeO2、Ga2O3In any or the combination of arbitrary two kinds.
In some embodiments, described property-modifying additive is institute in microwave-medium ceramics
The percentage by weight accounted for is 1wt%～5.0wt%.
In some embodiments, described property-modifying additive is institute in microwave-medium ceramics
The percentage by weight accounted for is 3wt%.
Present invention also offers the preparation method of a kind of microwave-medium ceramics, including following step
Rapid:
(1) ZrO is taken according to the stoichiometric proportion of the chemical expression of principal crystalline phase2、SnO2、
NiO、Ta2O5、TiO2After carry out for the first time being dried to obtain the first mixing after ball milling or husky mill
Thing；
(2) the first described mixture pre-burning is obtained powder；
(3) second time ball milling or sand are carried out after described powder being added property-modifying additive
Mill, obtains the second mixture after drying；
(4) described second mixture is added binding agent pelletize, compressing after prepare
Raw training；
(5) raw training described in is sintered obtains microwave-medium ceramics.
In some embodiments, in described step (2), the first mixture pre-burning obtains
Before powder, also include that the first mixture by described crosses the operation of 40 mesh sieves.
In some embodiments, in described step (4), the second mixture adds viscous
Mixture granulation, compressing rear preparing before life is trained also include the second described mixture mistake
The operation of 40 mesh sieves.
In some embodiments, in described step (2), the first mixture through 800 DEG C～
1000 DEG C of pre-burnings obtain powder；In described step (5), raw training is through 1300 DEG C～1360 DEG C
Sintering obtains microwave-medium ceramics.
In some embodiments, in described step (5), raw training is through 1340 DEG C of sintering
Obtain microwave-medium ceramics.
In some embodiments, in described step (1), ball milling or husky mill for the first time
Time is 8～16 hours；In described step (3), ball milling or husky time consuming for the second time
It it is 8～24 hours.
Compared with prior art, the microwave-medium ceramics that the present invention provides has the advantage that
(1) microwave dielectric property is preferable: DIELECTRIC CONSTANT εr=40～44, and in this scope
Interior scalable；Quality factor q *f=45000GHz～60000GHz；Frequency-temperature coefficient
τf=-8.5～+15.3 × 10-6/ DEG C in the range of scalable, temperature characterisitic is stable.
(2), in the preparation method of the microwave-medium ceramics that the present invention provides, sintering temperature is relatively
Low, save energy cost, meet the theory of low-carbon environment-friendly；
(3) preparation technology of the present invention is simple, it is not necessary to special installation and stringent process conditions,
It is suitable for industrialized production.
It follows that the microwave-medium ceramics that the present invention provides is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is (1-x) Zr0.5Sn0.5TiO4-x(Ni1/3Ta2/3)TiO4Microwave-medium ceramics
SEM schemes.
Detailed description of the invention
The claim of the present invention is done further by the mode below in conjunction with specific embodiment
Describing in detail, elaborating a lot of detail in the following description so that fully understanding
The present invention.
But the present invention can implement to be much different from alternate manner described here,
Those skilled in the art can do similar improvement in the case of intension of the present invention,
Therefore the present invention is not limited by following public being embodied as.
The invention provides a kind of microwave-medium ceramics, including principal crystalline phase, the change of principal crystalline phase
Learning expression formula is (1-x) Zr0.5Sn0.5TiO4-x(Ni1/3Ta2/3)TiO4, wherein (0.1≤x≤
0.3), wherein (Ni1/3Ta2/3)4+Interpolation significantly improve the quality factor of material and dielectric is normal
Number, can adjust temperature coefficient of resonance frequency simultaneously.
Above-mentioned, microwave-medium ceramics is in addition to belonging to ionic crystal structural polysilicon material, past
Toward still composite diphase material, generally by principal crystalline phase, one or more miscellaneous, pore etc. forms.
Wherein, Ti in principal crystalline phase4+、Zr4+、Ta5+The existence of ion and microwave-medium ceramics
High-k be correlated with, furthermore by regulation Sn4+Content can make frequency temperature system
Number τfIt is adjusted to zero.
It is to be appreciated that structure and the simple niobates of component are develop in recent years new
Type microwave dielectric ceramic materials, all of niobates is all columbite structure, and τfFor
Negative value.
Preferably, microwave ceramic dielectric material also includes property-modifying additive, described modification
Additive is MnO2、CeO2、Ga2O3In any or the combination of arbitrary two kinds.
Above-mentioned, ion substitution to the internal structure change of microwave ceramic dielectric material with produced
Raw corresponding dielectric properties change difference, by the phase structure of modified principal crystalline phase, aobvious
Micro-assembly robot, Analysis of Dielectric Properties, it appeared that different ionic radius, polarizability, electricity
The ion doping of negativity and valence state is relatively big to the performance impact of principal crystalline phase, the experiment proved that
MnO2、CeO2And Ga2O3Be respectively provided with improve microwave ceramic dielectric material dielectric properties,
Reduce the effect of sintering temperature.
Wherein, above-mentioned microwave-medium ceramics, by doping Mn ion, attracts free electron
It is changed into the electronics of tight-binding, the reduction of Ti ion can be suppressed, prevent sintered
Due to oxygen deficiency, Ti in journey4+It is reduced to Ti3+, thus cause dielectric loss to increase, micro-
The dielectric properties of ripple media ceramic deteriorate.
The study on the modification of host crystal system is mainly collected by lanthanide series Ce and boron group element Ga
In in ion pair crystal structure and the impact of dielectric properties.Meanwhile, by improving crystal knot
The compactness extent of crystal when structure also improves sintering pottery, thus reduce sintering temperature.
It is understood that the mode of doping vario-property additive is divided into two kinds: one to be first to close
Become principal crystalline phase compound, then doping vario-property additive；Two is at synthesis principal crystalline phase compound
The feed proportioning stage with regard to doping vario-property additive.
Preferably, the weight hundred that described property-modifying additive is shared in microwave-medium ceramics
Proportion by subtraction is 1wt%～5.0wt%.
Preferably, the weight hundred that described property-modifying additive is shared in microwave-medium ceramics
Proportion by subtraction is 3wt%.
Above-mentioned, the change in dielectric constant of composite diphase material obeys logarithm mixing rule, controls miscellaneous
Item content, particularly reduces air vent content, makes ceramics sample densified sintering product seem the heaviest
Want.
When property-modifying additive consumption should be avoided too high, the liquid that pottery produces in sintering process
Meet more, while promoting grain growth, also result in individual crystalline grains abnormal growth, brilliant
Particle size uniformity is deteriorated, and is unfavorable for the raising of density on the contrary, i.e. exceedes when amount of liquid phase
Good content is the most no longer beneficial to densification process.
When the addition of property-modifying additive controls within the specific limits, microwave-medium ceramics exists
During sintering, when consistency reaches preferably, being hardly visible pore, grain development is relatively complete,
Grain size concordance is preferable.But when exceeding certain value, the surface liquid of microwave-medium ceramics
Gradually increasing mutually, grain size concordance is poor, by the compactness of impact pottery.
The experiment proved that, above-mentioned microwave dielectric ceramic materials has low-loss and good micro-
Ripple dielectric properties DIELECTRIC CONSTANT ε=40～44, and scalable in this range；Quality factor
Q*f=45000GHz～60000GHz；Frequency-temperature coefficient τf=-8.5～+15.3 ×
10-6/ DEG C in the range of scalable, temperature characterisitic is stable.
The invention provides the preparation method of a kind of microwave-medium ceramics, comprise the following steps:
Step (1): take ZrO according to the stoichiometric proportion of the chemical expression of principal crystalline phase2、
SnO2、NiO、Ta2O5、TiO2After carry out being dried to obtain after ball milling or husky mill for the first time the
One mixture；
Above-mentioned, in step (1), it is preferable that be more than the ZrO of 99.5% with purity2、SnO2、
NiO、Ta2O5、TiO2For initial feed；Put into ball milling in ball mill.Ball milling for the first time
Purpose be to make powder refine and mixing all.
Preferably, initial feed is put in polyester tank, adds deionized water, adds zirconium ball,
Some hours of ball milling on planetary ball mill, rotating speed is 300～800 revs/min.
It is understood that deionized water can also be ethanol.
Preferably, initial feed, zirconium ball, the volume ratio of deionized water (ethanol) are
1:5:0.7～1.5.
Described planetary-type grinding machine is by ball grinder, fangs, rotating disk, fixed pulley and electricity
Motivations etc. form, and have four ball grinders on rotating disk, and when rotating disk rotates, ball grinder is with turning
Armor makees planetary motion around same axle center i.e. central shaft, and in tank, abrasive material is in high-speed motion
Grind and mix the raw material being submerged.This kind of ball grinder rotating speed is fast, and grinding efficiency is high, and structure is tight
Gather, easy to operate, seal sampling, safe and reliable, noise is low, pollution-free, lossless.
Of course, it should be understood that can also use other ball milling method and other
Mixer-mill.
It is to be understood that utilize high pure raw material, it is possible to reduce powder particle size, preparation ratio
The pure superfines that surface area is big, activity is high, can increase sintering power, promotes activity
Sintering, thus effectively reduce sintering temperature.
Preferably, the initial feed after ball milling is put in drying baker, in 100～120 DEG C of bakings
Dry.
Step (2): the first described mixture pre-burning is obtained powder.
Above-mentioned, the purpose of pre-burning is to allow native oxide carry out preliminary reaction, and
Crystallization needed for most of being formed, utilizes principal crystalline phase, and the contraction reducing porcelain becomes
Shape, the structure of feed change is beneficial to molding and sintering, thus improves the dielectricity of pottery
Can, to ensure the quality of final products.
When avoiding direct sintering after molding, ceramic shrinkage rate is big, and pottery easily deforms upon
Cracking etc..
Step (3): carry out after described powder is added property-modifying additive and sintering aid
Ball milling or husky mill, obtain the second mixture after drying for the second time；
Aforementioned, property-modifying additive mainly to microwave-medium ceramics dielectric properties main three
Parameter dielectric constant, quality factor and temperature coefficient of resonance frequency carry out improving and optimizing.
Microwave-medium ceramics is mainly made up of crystalline phase, crystal boundary, pore etc., belongs to ionic structure
Polycrystalline material.The rising of ceramic material density can with the increase of population in unit volume
To improve dielectric constant.Reduce the porosity, ceramic body sample sintering process can be formed perhaps
Many pores, this reduces one of major reason that density of material causes dielectric constant to decline just.
The another kind of method to the macro adjustments and controls dielectric constant of ceramic material is can to select not
Same radius size, the ion of different polarizability, by entering the A position of its principal phase, B position
Row ion exchange, so that unit cell volume changes with polarizability.The of ceramic material
Two-phase can affect the change of dielectric constant too, so controlling the growing amount of the second phase also
It it is one of the factor of important consideration.
It is experimentally verified that Mn4+、Ce4+And Ga3+Have and improve microwave ceramic dielectric material
Dielectric properties, the effect of reduction sintering temperature.
Preferably, the powder obtained after pre-burning, it is incubated 2～8 hours.
Furthermore, in step (3), second time ball milling makes, preburning powdered material and property-modifying additive
Mixing and refine, being likely to there is also in the powder after pre-burning does not has solid phase reversal complete
Initial feed, ball milling the most again, promote pilot process thing or initial feed to carry
Supply to increase the chance of reaction.
If there is no the secondary ball milling process after pre-burning, crystal grain will be caused relatively big and size not
All, also have impact on grain rearrangement and the densification of ceramic post sintering process.
Preferably, the powder after ball milling and property-modifying additive and the mixture of sintering aid
Put in drying baker, in 100～120 DEG C of drying.
Step (4): described second mixture is added binding agent pelletize, compressing
Rear prepared raw training.
Above-mentioned, pelletize is the leading technique of compressing；Because ceramic powder is more
Tiny, and powder is the thinnest, surface activity is the biggest, then the gas of its surface adsorption is also more
Many, thus its bulk density is the least, so the base after binding agent to be added raising dry-pressing
Body density.It is understood that the amount adding binding agent should be appropriate, cross molding at least
Difficulty, crosses the consistency that can reduce sample at most, affects its performance.
Adhesive can be polyvinyl alcohol (Polyvinyl alcohol, PVA), paraffin or phenol
Novolac.Being appreciated that in actual applications, adhesive can also be other kinds of
Adhesive.
Preferably, the polyvinyl alcohol that binding agent uses mass percent to be 8%～10%
(Polyvinyl alcohol, PVA) solution, carries out pelletize as binding agent, after pelletize
Crossing 80 mesh sieves, make green compact with powder compressing machine with the pressure of 4MPa, green compact are a diameter of
10mm, thickness is 5mm.
Preferably, binding agent uses mass percent to be 8% polyvinyl alcohol (Polyvinyl
Alcohol, PVA) solution.
Preferably, 80 mesh sieves are crossed after the second mixture adds binding agent pelletize.
Preferably, binder removal at a certain temperature is trained in life.
Unsuitable too fast it is understood that heat up during binder removal, cause Sheng Peinei to there is pore.
Preferably, by green compact at 600 DEG C of binder removal 4h, then according to the speed of 3～5 DEG C/min
Rate rises to temperature required during sintering some hours.
Step (5): described raw training is sintered obtains microwave-medium ceramics.
When improving sintering temperature, for the microwave-medium ceramics of 0.1≤x≤0.3, Q*f
Value is all first to increase, and then begins to decline or saturated.
Preferably, the microwave-medium ceramics prepared after sintering should cool down with sintering furnace.
In sum, the present invention provides the preparation method of microwave-medium ceramics to include step (1)
～step (5)；Utilize solid reaction process, by initial feed according to preset blending ratio physics
Method mix homogeneously, after pre-burning, adds property-modifying additive and improves the crystal of principal crystalline phase
Structure, when improve sintering raw training, the consistency in crystal, reduces pore, thus realizes
Step (5) is sintered to low-temp liquid-phase sintering, reduces the burning in solid reaction process
Junction temperature.The method technique is the most ripe, simple, with low cost, be easy to industry metaplasia
Produce, for the prefered method of industrialized production.
Preferably, in described step (2), the first mixture pre-burning is gone back before obtaining powder
Including the operation that the first described mixture is crossed 40 mesh sieves.
Above-mentioned, the first mixture disperses more uniform after sieving, the beneficially first mixture in
Pre-burning in step (3) is more abundant, is not susceptible to the phenomenons such as caking.
Preferably, in described step (4), the second mixture addition binding agent pelletize,
Also include that the second mixture by described crosses the behaviour of 40 mesh sieves before preparing raw training after compressing
Make.
Above-mentioned, the second mixture disperses more uniform after sieving, the beneficially second mixture in
Sintering in step (5) is more abundant, and the crystal grain in crystal is uniform, and pore is less and relatively
Little.
Preferably, in described step (2), the first mixture is through 800 DEG C～1000 DEG C
Pre-burning obtains powder；In described step (5), raw training is through 1300 DEG C～1360 DEG C sintering
Obtain microwave-medium ceramics.
Preferably, in described step (5), raw training obtains microwave through 1340 DEG C of sintering and is situated between
Matter pottery.
Above-mentioned, calcined temperature is unsuitable too high, and calcined temperature is too high, the reunion of preburning powdered material
Seriously, it is difficult to carry out secondary ball milling.Calcined temperature is too low, can affect ceramic post sintering process
Grain rearrangement and densification.
It is understood that sintering temperature should control within the specific limits, sintering temperature mistake
Low, crystal grain coarsening rate is the slowest, even cannot grow up.Along with sintering temperature improves crystal grain
Substantially growing up, grain circle gap is reduced, and grain development is abundant, and apparent porosity reduces.But
When sintering temperature is too high, crystal grain will appear from abnormal growth, and apparent porosity raises, crystal grain
The uniformity of growth, concordance decline.Meanwhile, excessive crystal grain is empty when Dislocations, oxygen
The probability that the defects such as position occur increases, and result in Q*fValue declines rapidly.
The most too high and sintering temperature and low excessively all can affect the normal growth of crystal grain.
Being verified by experiments, raw training obtains microwave-medium ceramics grain development through 1340 DEG C of sintering
Perfect, queueing discipline, pore is less, and compactness extent is preferable.
Preferably, in described step (2), the first mixture is through the powder of 1000 DEG C of pre-burnings
Material, is incubated 4 hours.
Preferably, in described step (5), raw training is incubated 6 after 1340 DEG C of sintering
Hour obtain microwave-medium ceramics.
Preferably, in described step (1), ball milling or husky time consuming for the first time be 8～
16 hours.
Preferably, in described step (1), ball milling or husky time consuming are 10 for the first time
Hour, rotating speed is 400 revs/min.
Preferably, in described step (3), ball milling or husky time consuming for the second time be 8～
24 hours.
Preferably, in described step (3), ball milling or husky time consuming are 16 for the second time
Hour, rotating speed is 400 revs/min.
Hereinafter, it is expanded on further by specific embodiment.
Specific embodiment and related process parameters refer to table 1.
Table 1
The test result of the relevant microwave dielectric property of specific embodiment refers to table 2.
Table 2
The microwave-medium ceramics that above-described embodiment 1～embodiment 12 prepare has good
Good microwave dielectric property: DIELECTRIC CONSTANT εr=40～42, and scalable in this range；
Quality factor q *f=45000GHz～60000GHz；Frequency-temperature coefficient τf=-8.5～
+15.3×10-6/ DEG C in the range of scalable, temperature characterisitic is stable.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes relatively
For concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.
It should be pointed out that, for the person of ordinary skill of the art, without departing from this
On the premise of bright design, it is also possible to make some deformation and improvement, these broadly fall into this
Bright protection domain.Therefore, the protection domain of patent of the present invention should be with claims
It is as the criterion.
Claims (10)
1. a microwave-medium ceramics, it is characterised in that: include principal crystalline phase, described oikocryst
The chemical expression of phase is (1-x) Zr0.5Sn0.5TiO4-x(Ni1/3Ta2/3) TiO, wherein (0.1
≤x≤0.3)。
2. microwave-medium ceramics as claimed in claim 1, it is characterised in that: also include
Property-modifying additive, described property-modifying additive is MnO2、CeO2、Ga2O3In arbitrary
A kind of combination of or arbitrary two kinds.
3. microwave-medium ceramics as claimed in claim 2, it is characterised in that: described
Property-modifying additive accounts for 1 in microwave-medium ceramics
Wt%～5.0wt%.
4. microwave-medium ceramics as claimed in claim 3, it is characterised in that: described
Property-modifying additive accounts for 3wt% in microwave-medium ceramics.
5. a preparation method for microwave-medium ceramics as claimed in claim 1, it is special
Levy and be:
(1) ZrO is taken according to the stoichiometric proportion of the chemical expression of principal crystalline phase2、SnO2、
NiO、Ta2O5、TiO2After carry out for the first time being dried to obtain the first mixing after ball milling or husky mill
Thing；
(2) the first described mixture pre-burning is obtained powder；
(3) second time ball milling or sand are carried out after described powder being added property-modifying additive
Mill, obtains the second mixture after drying；
(4) described second mixture is added binding agent pelletize, compressing after prepare
Raw training；
(5) raw training described in is sintered obtains microwave-medium ceramics.
6. the preparation method of microwave-medium ceramics as claimed in claim 5, its feature exists
In: in described step (2), the first mixture pre-burning also includes institute before obtaining powder
The first mixture stated crosses the operation of 40 mesh sieves.
7. the preparation method of microwave-medium ceramics as claimed in claim 5, its feature exists
In: in described step (4), the second mixture adds binding agent pelletize, compressing
Rear preparing before life is trained also includes that the second mixture by described crosses the operation of 40 mesh sieves.
8. the preparation method of microwave-medium ceramics as claimed in claim 5, its feature exists
In: in described step (2), the first mixture obtains through 800 DEG C～1000 DEG C of pre-burnings
Powder；In described step (5), raw training obtains microwave through 1300 DEG C～1360 DEG C of sintering
Media ceramic.
9. the preparation method of microwave-medium ceramics as claimed in claim 8, its feature exists
In: in described step (5), raw training obtains microwave-medium ceramics through 1340 DEG C of sintering.
10. the preparation method of microwave-medium ceramics as claimed in claim 5, its feature
Being: in described step (1), ball milling or husky time consuming are 8～16 hours for the first time；
In described step (3), ball milling or husky time consuming are 8～24 hours for the second time.
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| CN111384575A (en) * | 2018-12-31 | 2020-07-07 | 深圳市大富科技股份有限公司 | Dielectric filter, communication equipment, dielectric resonator and preparation method thereof |
| CN111384574A (en) * | 2018-12-31 | 2020-07-07 | 深圳市大富科技股份有限公司 | Dielectric filter, communication equipment, dielectric resonator and preparation method thereof |
| CN111384521A (en) * | 2018-12-31 | 2020-07-07 | 深圳市大富科技股份有限公司 | Dielectric filter, communication equipment, dielectric resonator and preparation method thereof |
| WO2024180832A1 (en) * | 2023-02-28 | 2024-09-06 | 株式会社村田製作所 | Dielectric ceramic and ceramic capacitor using same |
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