CN105669199A - Microwave dielectric ceramic and preparation method thereof - Google Patents

Microwave dielectric ceramic and preparation method thereof Download PDF

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CN105669199A
CN105669199A CN201610227052.1A CN201610227052A CN105669199A CN 105669199 A CN105669199 A CN 105669199A CN 201610227052 A CN201610227052 A CN 201610227052A CN 105669199 A CN105669199 A CN 105669199A
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microwave
medium ceramics
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sintering
ball milling
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CN105669199B (en
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张少林
崔立成
毛积闯
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Suzhou Zibo Electronic Technology Co Ltd
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Abstract

The invention provides a microwave dielectric ceramic and a preparation method thereof.The microwave dielectric ceramic comprises a main crystal phase.The chemical expression of the main crystal phase is Zr0.8Sn0.2-x(Mg1/3Nb2/3)xTiO4, wherein x is larger than 0 and smaller than or equal to 0.2.An experiment indicates that the microwave dielectric ceramic has good microwave dielectric performance, wherein the dielectric constant epsilon r can be adjusted within the range of 38 to 42; the quality factor Q*f is equal to 60,000 to 70,000 GHz; the frequency temperature coefficient tau f can be adjusted within the range of -2.5*10<-6>/DEG C to +6.3*10<-6>/DEG C, and the temperature characteristic is stable.The preparation method of the microwave dielectric ceramic is low in sintering temperature, energy cost is reduced, and the low carbon and environmental protection concept is met.The preparation process is simple, no special equipment or strict process condition is needed, and the microwave dielectric ceramic is suitable for industrial production.

Description

A kind of microwave-medium ceramics and preparation method thereof
Technical field
The invention belongs to electronically materials and component field, particularly relate 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 the critical material in the microwave devices such as wave filter, duplexer, resonator and Medium Wave Guide loop, is widely used in the microwave telecommunication devices such as satellite communication, mobile communication, electronic countermeasure and airborne communication, is one of the focus of current media material.
Zr0.8Sn0.2TiO4Pottery, as a kind of traditional microwave dielectric material, when microwave band is millimere-wave band (wave-length coverage: 1～10mm), has medium dielectric constant microwave medium (εr≈ 40), high quality factor q *f, nearly zero temperature coefficient of resonance frequency τfDeng microwave dielectric property, but there is sintering temperature height (higher than 1400 DEG C), in preparation process, energy consumption is relatively big, does not meet the theory of low-carbon environment-friendly.
Along with mobile communication technology development, miniaturization and high-quality to microwave device propose higher requirement, and it is claimed below that this just requires that microwave-medium ceramics dielectric material should meet: (1) has suitable medium dielectric constant microwave medium εr; (2) high quality factor Q*f; (3) temperature coefficient τfNearly zero; (4) low-carbon energy-saving. Therefore this area is necessary to provide microwave-medium ceramics that a kind of microwave dielectric property is better 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 Zr0.8Sn0.2-x(Mg1/3Nb2/3)xTiO4, wherein (0 < x≤0.2).
In some embodiments, also including sintering aid, described sintering aid is Li2O、B2O3、Bi2O3In any or several combination.
In some embodiments, also including property-modifying additive, described property-modifying additive is MnO2、Co2O3、Ga2O3In any or several combination.
In some embodiments, described principal crystalline phase molal weight percentage ratio shared by microwave-medium ceramics is 90～95mol%.
In some embodiments, described sintering aid molal weight percentage ratio shared by microwave-medium ceramics is 2.0～5.0mol%.
In some embodiments, described property-modifying additive molal weight percentage ratio shared by microwave-medium ceramics is 1.0～5.0mol%.
The preparation method that present invention also offers a kind of microwave-medium ceramics, comprises the following steps:
(1) ZrO is taken according to the stoichiometric proportion of the chemical expression of principal crystalline phase2、SnO2、MgO、Nb2O5、TiO2After carry out first time ball milling or husky mill after dry obtain the first mixture;
(2) the first described mixture pre-burning is obtained powder;
(3) carry out second time ball milling or husky mill after described powder being added property-modifying additive and sintering aid, obtain the second mixture after drying;
(4) the second described mixture is added binding agent pelletize, compressing rear prepared raw training;
(5) raw training described in is sintered obtains microwave-medium ceramics.
In some embodiments, in described step (2), the first mixture obtains powder through 800 DEG C～1000 DEG C pre-burnings; In described step (5), raw training obtains microwave-medium ceramics through 1200 DEG C～1300 DEG C sintering.
In some embodiments, in described step (1), first time ball milling or husky time consuming are 8～16 hours.
In some embodiments, in described step (3), second time ball milling or husky time consuming are 8～24 hours.
Compared with prior art, microwave-medium ceramics provided by the invention has the advantage that
(1) microwave dielectric property is better: DIELECTRIC CONSTANT εr=38～42, and within the scope of this scalable; Quality factor q *f=60000～70000GHz; Frequency-temperature coefficient τf=-2.5～+6.3 × 10-6/ DEG C, and within the scope of this scalable; Temperature characterisitic is stable;
(2) in the preparation method of microwave-medium ceramics provided by the invention, sintering temperature is relatively low, has saved energy cost, meets 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, is suitable for industrialized production.
It follows that microwave-medium ceramics provided by the invention is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is Zr0.8Sn0.2-x(Mg1/3Nb2/3)xTiO4The SEM figure of microwave-medium ceramics.
Detailed description of the invention
The claim of the present invention is described in further detail by the mode below in conjunction with specific embodiment, elaborates a lot of detail in the following description so that fully understanding the present invention.
But the present invention can implement being much different from alternate manner described here, and those skilled in the art can do similar improvement when without prejudice to intension of the present invention, therefore the present invention is by the following public restriction being embodied as.
The 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, the compositions such as microwave-medium ceramics is except belonging to ionic crystal structural polysilicon material, and also tending to is composite diphase material, generally by principal crystalline phase, one or more miscellaneous, pore.
Wherein, Sn4+、(Mg1/3Nb2/3)4+Ionic polarizability and ionic radius different, by Zr4+Replace and promote distortion of lattice thus improving quality factor, adjusting the purpose of dielectric constant, and by regulating Sn4+Content can make temperature coefficient of resonance frequency 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, all of niobates is all columbite structure, and τfFor negative value.
Preferably, microwave-medium ceramics also includes sintering aid, and described sintering aid is Li2O、B2O3、Bi2O3In any or several combination.
Above-mentioned, utilize admixture sintering aid to realize the low-temperature sintering of microwave-medium ceramics, relatively inexpensive, effective. Li2O、B2O3、Bi2O3Belonging to the oxide that fusing point is relatively low, the liquid phase produced during sintering accelerates the rearrangement of granule or crystal grain, thus reducing sintering temperature, namely forms active liquid phase sintering. Owing to the liquid phase existed between granule is thus creating huge capillary force during active liquid phase sintering, make granule generation sliding and rearrangement, capillary force produced by liquid phase also can cause the dissolving-precipitation process of solid phase particles simultaneously, makes less grain dissolution, bigger particle growth. At grain contact point, bigger capillary force makes solid-solution degree increase, material is just migrated to low solubility district by high-dissolvability district, so that the granule of contact area is gradually smooth and adjacent to each other, make base substrate shrink and reach densification, carry out comparatively dense sintering, decrease pore, reduce sintering temperature, thus carrying out low-temp liquid-phase sintering.
Preferably, microwave ceramic dielectric material also includes property-modifying additive MnO2、Co2O3、Ga2O3In any or several combination.
Above-mentioned, the internal structure change of microwave ceramic dielectric material is changed different with produced corresponding dielectric properties by ion substitution, by to the phase structure of modified principal crystalline phase, microstructure Analysis of Dielectric Properties, it appeared that the ion doping of different ionic radius, polarizability, electronegativity and valence state is relatively big to the performance impact of principal crystalline phase, the experiment proved that MnO2、Co2O3And Ga2O3The effect be respectively provided with the dielectric properties improving microwave ceramic dielectric material, reducing sintering temperature.
Wherein, above-mentioned microwave-medium ceramics, by the Mn ion that adulterates, attracts free electron to be changed into the electronics of tight-binding, it is possible to suppress the reduction of Ti ion, it is prevented that owing to oxygen is not enough in sintering process, Ti4+It is reduced to Ti3+, thus causing that dielectric loss increases, the dielectric properties of microwave-medium ceramics worsen.
Preferably, described principal crystalline phase total content in microwave dielectric ceramic materials is 90～95mol%.
Preferably, described sintering aid molar percentage shared by microwave dielectric ceramic materials is 2.0～5.0mol%.
Above-mentioned, the change in dielectric constant of composite diphase material obeys logarithm mixing rule, controls miscellaneous content, particularly reduces air vent content, makes ceramics sample densified sintering product be particularly important.
When the consumption of sintering aid is too high, the liquid phase that pottery produces in sintering process can be more, individual crystalline grains abnormal growth is also resulted in while promoting grain growth, even grain size is deteriorated, it is unfavorable for the raising of density on the contrary, is namely also no longer beneficial to densification process when amount of liquid phase exceedes optimum content.
Preferably, described property-modifying additive molar percentage shared by microwave dielectric ceramic materials is 1.0～5.0mol%.
Above-mentioned, it is to be understood that the mode of doping vario-property additive is divided into two kinds: one to be first synthesize principal crystalline phase compound then doping vario-property additive; Two be synthesis principal crystalline phase compound the feed proportioning stage with regard to doping vario-property additive.
Preferably, described 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 is 1～1.5mol%.
Above-mentioned, B2O3The effect reducing sintering temperature is best, but needs to control its ratio in sintering aid, thus preventing the deterioration of microwave-medium ceramics dielectric properties; Li2O、B2O3、Bi2O3The molal weight percentage ratio of three in proper range, while controlling dielectric loss, should reduce temperature during sintered microwave dielectric pottery.
Preferably, described 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, when sintering, when consistency reaches preferably, is hardly visible pore, and grain development is relatively complete, and grain size concordance is better. But when exceeding certain value, the surface liquid phase of microwave-medium ceramics increases gradually, and 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 microwave dielectric property DIELECTRIC CONSTANT ε=38～42, and within the scope of this scalable; Quality factor q *f=60000～70000GHz; Frequency-temperature coefficient τf=-2.5～+6.3 × 10-6/ DEG C within the scope of scalable, temperature characterisitic is stable.
The preparation method that the invention provides a kind of microwave-medium ceramics, comprises the following steps:
Step (1): take ZrO according to the stoichiometric proportion of the chemical expression of principal crystalline phase2、SnO2、MgO、Nb2O5、TiO2After carry out first time ball milling or husky mill after dry obtain the first mixture;
Above-mentioned, in step (1), it is preferable that with the purity ZrO more than 99%2、SnO2、MgO、Nb2O5, and the purity TiO more than 99.9%2For initial feed; Put into ball milling in ball mill. First time ball milling in order that make powder refine and mix equal.
Preferably, initial feed is put in polyester tank, adds deionized water, adds zirconium ball, and ball milling some hours 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, deionized water (ethanol) volume ratio be 1:5:0.7～1.5.
Described planetary-type grinding machine is made up of ball grinder, fangs, rotating disk, fixed pulley and motor etc., rotating disk has four ball grinders, when rotating disk rotates, ball grinder makes planetary motion with rotating disk around same axle center and central shaft, and in tank, abrasive material grinds in high-speed motion and mixes the raw material being submerged. This kind of ball grinder rotating speed is fast, and grinding efficiency is high, and compact conformation is easy to operate, seals sampling, and safe and reliable, noise is low, pollution-free, lossless.
Of course, it should be understood that other ball milling method and other mixer-mill can also be adopted.
It is to be understood that utilize high pure raw material, it is possible to reduce powder particle size, the pure superfines that preparation specific surface area is big, activity is high, it is possible to increasing sintering power, promoting reactive sintering, thus effectively reducing sintering temperature.
Preferably, the initial feed after ball milling is put in drying baker, in 100～120 DEG C of drying, then crosses 40 mesh sieves, and the initial feed after sieving is uniformly dispersed, it is simple to pre-burning.
Step (2): the first described mixture pre-burning is obtained powder.
Above-mentioned, pre-burning in order that allow native oxide carry out preliminary reaction, and major part can form required Crystallization, utilize principal crystalline phase, reduce the contraction distortion of porcelain, the structure of feed change is beneficial to molding and sintering, thus improving the dielectric properties of pottery, 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 second time ball milling or husky mill after described powder is added property-modifying additive and sintering aid, obtain the second mixture after drying;
Aforementioned, main three parameter dielectric constants of microwave-medium ceramics dielectric properties, quality factor and temperature coefficient of resonance frequency are mainly improved and optimize by property-modifying additive. Microwave-medium ceramics is mainly made up of crystalline phase, crystal boundary, pore etc., belongs to the polycrystalline material of ionic structure. The rising of ceramic material density can improve dielectric constant with the increase of population in unit volume. Reducing the porosity, can form many pores in ceramic body sample sintering process, 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 to select the ion of different radii size, different polarizability, by the A position of its principal phase, B position are carried out ion exchange, so that unit cell volume and polarizability change. The second-phase of ceramic material can affect the change of dielectric constant too, so the growing amount controlling second-phase is also one of factor of important consideration.
It is experimentally verified that Mn4+、Co3+And Ga3+The effect there are the dielectric properties improving microwave ceramic dielectric material, reducing 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 mixes with property-modifying additive and sintering aid and refines, being likely to there is also in powder after pre-burning does not have solid phase reversal initial feed completely, at this moment ball milling again, promotes pilot process thing or initial feed to provide the chance increasing reaction.
If there is no the secondary ball milling process after pre-burning, will cause that crystal grain is relatively big and size is uneven, also have impact on the grain rearrangement of ceramic post sintering process and densification.
Preferably, the mixture of the powder after ball milling and property-modifying additive and sintering aid is put in drying baker, in 100～120 DEG C of drying, then crosses 40 mesh sieves, is uniformly dispersed.
Step (4): the second described mixture is added binding agent pelletize, compressing rear prepared raw training.
Above-mentioned, pelletize is a compressing leading technique; Because ceramic powder is comparatively fine, and powder is more thin, and surface activity is more big, then the gas of its surface adsorption is also more many, thus its bulk density is also more little, so to add the blank density after binding agent raising dry-pressing. It is understood that the amount adding binding agent should be appropriate, cross difficult forming at least, cross the consistency that can reduce sample at most, affect its performance.
Adhesive can be polyvinyl alcohol (Polyvinylalcohol, PVA), paraffin or novolaks. Being appreciated that in actual applications, adhesive can also be other kinds of adhesive.
Preferably, polyvinyl alcohol (Polyvinylalcohol, the PVA) solution that binding agent adopts mass percent to be 8%～10%, carry out pelletize as binding agent, cross 80 mesh sieves after pelletize, make green compact with powder compressing machine with the pressure of 4MPa, green compact diameter is 10mm, and thickness is 5mm.
Preferably, binding agent adopts mass percent to be 8% polyvinyl alcohol (Polyvinylalcohol, PVA) solution.
Preferably, the second mixture crosses 80 mesh sieves after adding binding agent pelletize.
Preferably, binder removal at a certain temperature is trained in life.
It is understood that it is unsuitable too fast to heat up during binder removal, Sheng Peinei is caused 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 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 < x≤0.2, Q*fValue is all first 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 the initial feed method mix homogeneously according to preset blending ratio physics, after pre-burning, add property-modifying additive and improve the crystal structure of principal crystalline phase, it is simultaneously introduced the consistency that sintering aid improves during sintering life training in crystal, reduce pore, it is achieved thereby that step (5) is sintered to low-temp liquid-phase sintering, reduce the sintering temperature in solid reaction process. The method technique is very ripe, simple, with low cost, be easy to industrialized production, for the prefered method of industrialized production.
Preferably, in described step (2), the first mixture obtains powder through 800 DEG C～1000 DEG C pre-burnings; In described step (5), raw training obtains microwave-medium ceramics through 1200 DEG C～1300 DEG C sintering.
Above-mentioned, calcined temperature is unsuitable too high, and calcined temperature is too high, and the reunion of preburning powdered material is serious, it is difficult to carry out secondary ball milling. Calcined temperature is too low, can affect grain rearrangement and the densification of ceramic post sintering process.
Furthermore, sintering temperature should control within the specific limits, and sintering temperature is too low, and grain growth speed is excessively slow, even cannot grow up. Substantially growing up along with sintering temperature improves crystal grain, 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, apparent porosity raises, and the uniformity of grain growth, concordance decline. Meanwhile, the probability that excessive crystal grain occurs when the defect such as Dislocations, Lacking oxygen increases, and result in Q*fValue declines rapidly.
Therefore too high and mistake sintering temperature and low all can affect the normal growth of crystal grain.
Preferably, in described step (2), the first mixture obtains powder through 900 DEG C of pre-burnings; In described step (5), raw training obtains microwave-medium ceramics through 1260 DEG C of sintering.
Preferably, in described step (2), the first mixture, through the powder of 900 DEG C of pre-burnings, is incubated 4 hours.
Preferably, in described step (5), raw training insulation after 1260 DEG C sinter obtains microwave-medium ceramics in 6 hours.
Preferably, in described step (1), first time ball milling or husky time consuming are 8～16 hours.
Preferably, in described step (1), first time ball milling or husky time consuming are 10 hours, and rotating speed is 400 revs/min.
Preferably, in described step (3), second time ball milling or husky time consuming are 8～24 hours.
Preferably, in described step (3), second time ball milling or husky time consuming are 16 hours, and 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
Embodiment DIELECTRIC CONSTANT 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 above-described embodiment 1～embodiment 12 prepares has good microwave dielectric property: DIELECTRIC CONSTANT εr=38～42, and within the scope of this scalable; Quality factor q *f=60000～70000GHz; Frequency-temperature coefficient τf=-2.5～+6.3 × 10-6/ DEG C within the scope of scalable, temperature characterisitic is stable.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes comparatively 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 the inventive concept of the premise, it is also possible to making some deformation and improvement, these broadly fall into protection scope of the present invention. Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a microwave-medium ceramics, it is characterised in that: including principal crystalline phase, the chemical expression of described principal crystalline phase is Zr0.8Sn0.2-x(Mg1/3Nb2/3)xTiO4, wherein (0 < x≤0.2).
2. microwave-medium ceramics as claimed in claim 1, it is characterised in that: also including sintering aid, described sintering aid is Li2O、B2O3、Bi2O3In any or several combination.
3. microwave-medium ceramics as claimed in claim 1, it is characterised in that: also including property-modifying additive, described property-modifying additive is MnO2、Co2O3、Ga2O3In any or several combination.
4. microwave-medium ceramics as claimed in claim 1, it is characterised in that: described principal crystalline phase molal weight percentage ratio shared by microwave-medium ceramics is 90～95mol%.
5. microwave-medium ceramics as claimed in claim 2, it is characterised in that: described sintering aid molal weight percentage ratio shared by microwave-medium ceramics is 2.0～5.0mol%.
6. microwave-medium ceramics as claimed in claim 3, it is characterised in that: described property-modifying additive molal weight percentage ratio shared by microwave-medium ceramics is 1.0～5.0mol%.
7. the preparation method of a microwave-medium ceramics as claimed in claim 1, it is characterised in that:
(1) ZrO is taken according to the stoichiometric proportion of the chemical expression of principal crystalline phase2、SnO2、MgO、Nb2O5、TiO2After carry out first time ball milling or husky mill after dry obtain the first mixture;
(2) the first described mixture pre-burning is obtained powder;
(3) carry out second time ball milling or husky mill after described powder being added property-modifying additive and sintering aid, obtain the second mixture after drying;
(4) the second described mixture is added binding agent pelletize, compressing rear prepared raw training;
(5) raw training described in is sintered obtains microwave-medium ceramics.
8. the preparation method of microwave-medium ceramics as claimed in claim 7, it is characterised in that: in described step (2), the first mixture obtains powder through 800 DEG C～1000 DEG C pre-burnings; In described step (5), raw training obtains microwave-medium ceramics through 1200 DEG C～1300 DEG C sintering.
9. the preparation method of microwave-medium ceramics as claimed in claim 7, it is characterised in that: in described step (1), first time ball milling or husky time consuming are 8～16 hours.
10. the preparation method of microwave-medium ceramics as claimed in claim 7, it is characterised in that: in described step (3), second time ball milling or husky time consuming are 8～24 hours.
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