CN106220166B - A kind of microwave-medium ceramics and preparation method thereof - Google Patents

A kind of microwave-medium ceramics and preparation method thereof Download PDF

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CN106220166B
CN106220166B CN201610552817.9A CN201610552817A CN106220166B CN 106220166 B CN106220166 B CN 106220166B CN 201610552817 A CN201610552817 A CN 201610552817A CN 106220166 B CN106220166 B CN 106220166B
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microwave
medium ceramics
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CN106220166A (en
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殷旺
吕开明
马才兵
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GUANGDONG GOVA ADVANCED MATERIAL TECHNOLOGY Co Ltd
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Abstract

The invention belongs to microwave-medium ceramics technical field, more particularly to a kind of microwave-medium ceramics and preparation method thereof.The microwave-medium ceramics have following chemical general formula：Ba2Zn4xTi8‑ 2yNb2yO18+4x+y, x=0.1~0.7, y=0~0.01；Also include 0~1wt% additive.Between the microwave-medium ceramics dielectric constant of the present invention is 30~40, Q × f>46000GHz, up to 66700GHz, compared to other system microwave-medium ceramics of same dielectric constant, body series Q × f values are big, and dielectric loss is low, temperature coefficient of resonance frequency continuously adjustabe between 20PPM/ DEG C~+17PPM/ DEG C.Present invention also offers the preparation method of above-mentioned microwave-medium ceramics, and the preparation method is simple, and sintering temperature is low, only needs 1100~1300 DEG C, and meets environmental requirement, nontoxic, environmentally safe.

Description

A kind of microwave-medium ceramics and preparation method thereof
Technical field
The invention belongs to microwave-medium ceramics technical field, more particularly to a kind of microwave-medium ceramics and preparation method thereof.
Background technology
With the continuous development of modern communication technology, mobile operator will face the 2G networks such as GSM, CDMA, WCDMA, Different systems caused by the 4G network integration networkings such as the 3G networks such as CDMA2000, TD-SCDMA and TD-LTE, FDD-LTE, phase Severe jamming between adjacent frequency section, the dielectric filter of excellent performance obtain extensive concern, and also just microwave-medium ceramics are proposed Dielectric constant is high, Qf is high, the requirement of temperature coefficient of resonance frequency continuously adjustabe.Middle high-permittivity microwave medium ceramics, its It is worth between 30 to 40, to be mainly used in 1GHz~8GHz microwave military radar, satellite communication and the mobile communication of communication system In base station.Such ceramic developmental research contributes to the systematization of microwave-medium ceramics system, integration.Study at present more Ba(Zn1/3Nb2/3)O3System, Ba (Co1/3Nb2/3)O3System, Ba [(Zn, Co)1/3Nb2/3]O3System etc., but due to cost too Height limits its extensive commercialization.
The content of the invention
The shortcomings that in order to overcome above-mentioned prior art microwave-medium ceramics cost too high and deficiency, primary and foremost purpose of the invention It is to provide a kind of inexpensive microwave-medium ceramics.
Another object of the present invention is to provide a kind of preparation method of above-mentioned microwave-medium ceramics.
The purpose of the present invention is realized by following proposal：
A kind of microwave-medium ceramics, there is following chemical general formula：Ba2Zn4xTi8-2yNb2yO18+4x+y, x=0.1~0.7, y =0~0.01.
Above-mentioned microwave-medium ceramics also include 0~1wt% additive.
Above-mentioned microwave-medium ceramics, including with BaCO3, ZnO and TiO2Based on, and with part Nb5+Replace Ti4+It is compound and Into.
Above-mentioned microwave-medium ceramics, between dielectric constant is 30~40, Q × f>46000GHz, up to 66700GHz, phase Than in other system microwave-medium ceramics of same dielectric constant, body series Q × f values are big, and dielectric loss is low, resonant frequency temperature system Number continuously adjustabe between -20PPM/ DEG C~+17PPM/ DEG C.
The present invention also provides a kind of preparation method of above-mentioned microwave-medium ceramics, comprises the following steps：
According to Ba2Zn4xTi8-2yNb2yO18+4x+yStoichiometric proportion, wherein, x=0.1~0.7, y=0~0.01, will BaCO3、ZnO、Nb2O5And TiO2Dispensing in proportion, a ball milling and drying obtain mixed once material；Preheating, obtain pre-burning Material；Binding agent is added, after granulating and forming, obtains ceramic green；Sintering, obtains microwave-medium ceramics.
When containing additive in the microwave-medium ceramics, preparation method is further comprising the steps of：
Additive is added into the Preburning material being prepared, is dried after secondary ball milling, obtains secondary mixed material, is added viscous Tie agent and carry out subsequent treatment.
The addition of the additive is the 0~1% of Preburning material quality.
In one of the embodiments, the preparation method of the additive is：
By SiO2、B2O3, CaO, CuO and Y2O3Ball milling after mixing, 10~30min is melted in 1300~1400 DEG C, obtains institute State additive.
In one of the embodiments, SiO used2、B2O3, CaO, CuO and Y2O3Mass ratio be (40~55):(25~ 35):(15~30):(2~10):(1~10).
In one of the embodiments, SiO used2、B2O3, CaO, CuO and Y2O3Mass ratio be 45:30:18:5:2.
In one of the embodiments, the technique of the ball milling is：Institute's materials：Ball：Water=1:(3~4):The matter of (2~3) Ratio, 200~300r/min of rotating speed are measured, Ball-milling Time is 20~24 hours.
In one of the embodiments, powder carries out melt process again after drying, sieving after the ball milling.
In one of the embodiments, the product obtained after the melting is through separating, crushing, the operation such as sieve is refined Product used again.
In the preparation method of above-mentioned microwave-medium ceramics：
In one of the embodiments, the technique of a ball milling is specially：Institute's materials：Ball：Water=1:(3~4):(2 ~3) mass ratio, 200~300r/min of rotating speed, ball milling 3~5 hours；More specifically：In planetary ball mill, with zirconium ball As abrading-ball, deionized water is as ball-milling medium, according to material：Ball：Water=1:3:2 quality is than ball milling 3~5 hours, the ball The rotating speed of mill is 250r/min.
In one of the embodiments, the preheating, in the step of obtaining Preburning material, the condition of the pre-burning is： With 3~8 DEG C/min heating rate, 800~1000 DEG C are warming up to, insulation cools down after 3~4 hours.
In one of the embodiments, the technique of the secondary ball milling is specially：Institute's materials：Ball：Water=1:(3~4):(2 ~3) mass ratio, 200~300r/min of rotating speed, ball milling 3~5 hours；More specifically：In planetary ball mill, with zirconium ball As abrading-ball, deionized water is as ball-milling medium, according to mixed once material：Ball：Water=1:3:2 quality is smaller than ball milling 3~5 When, the rotating speed of the ball milling is 250r/min.
In one of the embodiments, described binding agent is that the polyvinyl alcohol that weight/mass percentage composition is 6~8% is water-soluble Liquid；The addition of the binding agent is the 15~25% of reaction system gross mass.
In one of the embodiments, the condition of the sintering is：1100 are warming up to 3~8 DEG C/min heating rate ~1300 DEG C, insulation cools down after 2~4 hours.
In one of the embodiments, described drying is to be dried at 80~150 DEG C.
Between the microwave-medium ceramics dielectric constant of the present invention is 30~40, Q × f>46000GHz, up to 66700GHz, compared to other system microwave-medium ceramics of same dielectric constant, body series Q × f values are big, and dielectric loss is low, humorous Vibration frequency temperature coefficient continuously adjustabe between -20PPM/ DEG C~+17PPM/ DEG C.Its preparation method is simple, and sintering temperature is low, only 1100~1300 DEG C are needed, and meets environmental requirement, it is nontoxic, environmentally safe.
Brief description of the drawings
Fig. 1 is microwave-medium ceramics Ba of the present invention2Zn4xTi8-2yNb2yO18+4x+yPreparation flow figure.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, below in conjunction with the accompanying drawings to the present invention Embodiment be described in detail.Many details are elaborated in the following description in order to fully understand this hair It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not Similar improvement is done in the case of running counter to intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
In present embodiment, the content by adjusting Zn can realize the adjustment between the 30~40 of dielectric constant, frequency The continuously adjustabe of temperature coefficient, and the larger Q values for improving body series, reduce sintering temperature.Nb5+Replace Ti4+Ti will be suppressed Reduction, rock-steady structure, further lifted Qf values.The introducing of additive reduces sintering temperature, suppresses Ti reduction, lifts Qf Value.
Specific preparation flow figure is referring to Fig. 1, the preparation method of the microwave-medium ceramics of an embodiment, including following step Suddenly：
S310, by BaCO3、ZnO、Nb2O5And TiO2Dispensing in proportion, ball milling simultaneously obtain once in 80 DEG C~150 DEG C drying Compound.
Preferably, drying temperature is 120 DEG C.
Wherein, the method for ball milling is specially：In planetary ball mill, using zirconium ball as abrading-ball, deionized water is as ball Grinding media, according to mixed once material：Zirconium ball：Deionized water=1:3:2 quality was than ball milling 3~5 hours.Preferably, ball milling Rotating speed is 250r/min.
It is appreciated that in other embodiments, ball milling can also use the ball mill and ball-milling technology of other forms, but It is preferably planetary ball mill in the present embodiment.
S320, by the mixed once material progress preheating obtain Preburning material.
Preferably, the condition of pre-burning is：With 3 DEG C/min heating rate, 800 DEG C~1000 DEG C are warming up to, insulation 3~4 Cooled down after hour.
S330, the Preburning material is added and dried after additive ball milling at 80 DEG C~150 DEG C, obtain secondary mixed material.
Preferably, drying temperature is 120 DEG C.
Wherein, the method for ball milling is specially：In planetary ball mill, using zirconium ball as abrading-ball, deionized water is as ball Grinding media, according to mixed once material：Zirconium ball：Deionized water=1:3:2 quality was than ball milling 3~5 hours.Preferably, ball milling Rotating speed is 250r/min.
It is appreciated that in other embodiments, ball milling can also use the ball mill and ball-milling technology of other forms, but It is preferably planetary ball mill in the present embodiment.
S340, obtain ceramic green after adding binding agent granulating and forming in the secondary mixed material.
In present embodiment, the binding agent is the polyvinyl alcohol water solution that weight/mass percentage composition is 6%.Polyvinyl alcohol passes through Become CO after high-temperature calcination2And H2O, can all it volatilize.Preferably, the addition of the binding agent is the secondary mixed material matter The 15~25% of amount.
It is appreciated that can also be other binding agents in other embodiments, such as any bonding commonly used in the art Agent, as long as there is enough stickiness, it is ensured that good mouldability and the mechanical strength of base substrate, and can all be waved after high-temperature calcination Hair, makes not leaving glue residue impurity in base substrate.
The step of granulation aftershaping obtains microwave-medium ceramics green compact is concretely：The secondary mixed of binding agent will be added Close material, be granulated grinding 1 hour, cross 80 mesh sieve, then under 80~120MPa pressure by powder pressing into diameter height ratio about For 2.0 cylinder.Preferably, the pressure is 100MPa.
S350, by the ceramic green 1100 DEG C~1300 DEG C sintering, obtain microwave-medium ceramics.
Preferably, it is by the condition of microwave-medium ceramics green sintering：1100 DEG C are warming up to 3 DEG C/min heating rate ~1300 DEG C, insulation cools down after 2~4 hours.
The preparation method of additive is：
By SiO2、B2O3, CaO, CuO and Y2O3After mixing after ball milling, drying, sieving, 10~30min is melted in 1350 DEG C, The additive is obtained after separation, broken, sieving.
Preferable SiO2、B2O3, CaO, CuO and Y2O3Mass ratio be 45:30:18:5:2.Ball-milling Time is 24 hours.
Separation method is to carry out extract and separate with deionized water, and sieving is the sieve with 200 mesh.
The addition of preferable additive is the 0~1% of Preburning material quality.
It is as follows to the method for testing of above-mentioned microwave-medium ceramics：Sample surfaces are polished, using Agilent5061B networks Analyzer, permittivity ε is determined according to Hakki-Coleman methodsrAnd quality factor q.
The preparation method of above-mentioned microwave-medium ceramics is simple, and sintering temperature is low, and meets environmental requirement, nontoxic, to environment It is pollution-free.
It is specific embodiment below, agents useful for same can obtain from commercial channel.
Embodiment 1
X=0.25, y=0 is taken to weigh 88.4887g BaCO3, 18.2466g ZnO and 143.2645g TiO2.By the title Raw material, zirconium ball and the deionized water taken is with 1:3:2 mass ratio, with planetary mills wet ball grinding 4 hours, after 120 DEG C of drying, In 950 DEG C of pre-burnings 3 hours (in air atmosphere), heating rate is 3 DEG C/min, furnace cooling, obtains Preburning material.
By the Preburning material, zirconium ball and deionized water with 1:3:2 mass ratio, with planet wet ball grinding 4 hours, 120 DEG C drying after obtain Microwave dielectric ceramic powder material.20% bonding of powder quality is added in the Microwave dielectric ceramic powder material Agent, grinding 1 hour is granulated, crosses the sieve of 80 mesh, by powder pressing Cheng Houwei 6mm, a diameter of 13mm thin cylinder base substrate, pressure is 100MPa, sinter base substrate into porcelain at 1250 DEG C, heating rate is 3 DEG C/min, soaking time 3h, then furnace cooling, is obtained To microwave-medium ceramics.
Test to prepared microwave-medium ceramics is as follows：
Prepared ceramics sample is polished by metallographic, flannelette dielectric surface, using Agilent 5061B network analysis Instrument, permittivity ε is determined according to Hakki-Coleman methodsrWith tan δ, and quality factor q f is calculated.In addition, resonant frequency The measure of temperature coefficient is to be joined directly together Network Analyzer and insulating box, tests the resonance within the temperature range of 20 DEG C~85 DEG C The changing value of frequency, then calculates τ according to equation belowfValue, the results are shown in Table 1.
Embodiment 2
X=0.25, y=0.005 is taken to weigh 88.4046g BaCO3, 18.2292g ZnO, 142.7705g TiO2With 0.5954g Nb2O5.By the raw material weighed, zirconium ball and deionized water with 1:3:2 mass ratio, with planetary mills wet method ball Mill 4 hours, after 120 DEG C of drying, in 950 DEG C of pre-burnings 3 hours (in air atmosphere), heating rate is 3 DEG C/min, cold with stove But, Preburning material is obtained.
By the Preburning material, zirconium ball and deionized water with 1:3:2 mass ratio, with planet wet ball grinding 4 hours, 120 DEG C drying after obtain Microwave dielectric ceramic powder material.20% bonding of powder quality is added in the Microwave dielectric ceramic powder material Agent, grinding 1 hour is granulated, crosses the sieve of 80 mesh, by powder pressing Cheng Houwei 6mm, a diameter of 13mm thin cylinder base substrate, pressure is 100MPa, sinter base substrate into porcelain at 1250 DEG C, heating rate is 3 DEG C/min, soaking time 3h, then furnace cooling, is obtained To microwave-medium ceramics.
Performance test is carried out to prepared microwave-medium ceramics, method the results are shown in Table 1 with embodiment 1.
Embodiment 3
X=0.25, y=0.01 is taken to weigh 88.3207g BaCO3, 18.2119g ZnO, 142.2775g TiO2With 1.1897g Nb2O5.By the raw material weighed, zirconium ball and deionized water with 1:3:2 mass ratio, with planetary mills wet method ball Mill 4 hours, after 120 DEG C of drying, in 950 DEG C of pre-burnings 3 hours (in air atmosphere), heating rate is 3 DEG C/min, cold with stove But, Preburning material is obtained.
By the Preburning material, zirconium ball and deionized water with 1:3:2 mass ratio, with planet wet ball grinding 4 hours, 120 DEG C drying after obtain Microwave dielectric ceramic powder material.20% bonding of powder quality is added in the Microwave dielectric ceramic powder material Agent, grinding 1 hour is granulated, crosses the sieve of 80 mesh, by powder pressing Cheng Houwei 6mm, a diameter of 13mm thin cylinder base substrate, pressure is 100MPa, sinter base substrate into porcelain at 1250 DEG C, heating rate is 3 DEG C/min, soaking time 3h, then furnace cooling, is obtained To microwave-medium ceramics.
Performance test is carried out to prepared microwave-medium ceramics, method the results are shown in Table 1 with embodiment 1.
The microwave dielectric ceramic performance of 1 embodiment of table 1~3
Numbering x y εr Qf(GHz) τf(PPM/℃)
Embodiment 1 0.25 0 36.11 48700 -0.2
Embodiment 2 0.25 0.005 36.41 54000 +0.2
Embodiment 3 0.25 0.01 36.75 46000 +0.3
Embodiment 4
X=0.25, y=0.005 is taken to weigh 88.4046g BaCO3, 18.2292g ZnO, 142.7705g TiO2With 0.5954g Nb2O5.By the raw material weighed, zirconium ball and deionized water with 1:3:2 mass ratio, with planetary mills wet method ball Mill 4 hours, after 120 DEG C of drying, in 950 DEG C of pre-burnings 3 hours (in air atmosphere), heating rate is 3 DEG C/min, cold with stove But, Preburning material is obtained.Preburning material is mixed with additive, obtains the amount of the mixture of Preburning material and additive, wherein additive For the 0.2% of Preburning material quality.
By the mixture of the Preburning material and additive, zirconium ball and deionized water with 1:3:2 mass ratio, with planet wet method Ball milling 4 hours, Microwave dielectric ceramic powder material is obtained after 120 DEG C of drying.Powder is added in the Microwave dielectric ceramic powder material 20% adhesive of quality, grinding 1 hour is granulated, crosses the sieve of 80 mesh, by powder pressing Cheng Houwei 6mm, a diameter of 13mm Thin cylinder base substrate, pressure 100MPa, sinter base substrate into porcelain at 1150 DEG C, heating rate is 3 DEG C/min, and soaking time is 3h, then furnace cooling, obtains microwave-medium ceramics.
Performance test is carried out to prepared microwave-medium ceramics, method the results are shown in Table 2 with embodiment 1.
Embodiment 5
X=0.25, y=0.005 is taken to weigh 88.4046g BaCO3, 18.2292g ZnO, 142.7705g TiO2With 0.5954g Nb2O5.By the raw material weighed, zirconium ball and deionized water with 1:3:2 mass ratio, with planetary mills wet method ball Mill 4 hours, after 120 DEG C of drying, in 950 DEG C of pre-burnings 3 hours (in air atmosphere), heating rate is 3 DEG C/min, cold with stove But, Preburning material is obtained.Preburning material is mixed with additive, obtains the amount of the mixture of Preburning material and additive, wherein additive For the 0.6% of Preburning material quality.
By the mixture of the Preburning material and additive, zirconium ball and deionized water with 1:3:2 mass ratio, with planet wet method Ball milling 4 hours, Microwave dielectric ceramic powder material is obtained after 120 DEG C of drying.Powder is added in the Microwave dielectric ceramic powder material 20% adhesive of quality, grinding 1 hour is granulated, crosses the sieve of 80 mesh, by powder pressing Cheng Houwei 6mm, a diameter of 13mm Thin cylinder base substrate, pressure 100MPa, sinter base substrate into porcelain at 1150 DEG C, heating rate is 3 DEG C/min, and soaking time is 3h, then furnace cooling, obtains microwave-medium ceramics.
Performance test is carried out to prepared microwave-medium ceramics, method the results are shown in Table 2 with embodiment 1.
Embodiment 6
X=0.25, y=0.005 is taken to weigh 88.4046g BaCO3, 18.2292g ZnO, 142.7705g TiO2With 0.5954g Nb2O5.By the raw material weighed, zirconium ball and deionized water with 1:3:2 mass ratio, with planetary mills wet method ball Mill 4 hours, after 120 DEG C of drying, in 950 DEG C of pre-burnings 3 hours (in air atmosphere), heating rate is 3 DEG C/min, cold with stove But, Preburning material is obtained.Preburning material is mixed with additive, obtains the amount of the mixture of Preburning material and additive, wherein additive For the 1% of Preburning material quality.
By the mixture of the Preburning material and additive, zirconium ball and deionized water with 1:3:2 mass ratio, with planet wet method Ball milling 4 hours, Microwave dielectric ceramic powder material is obtained after 120 DEG C of drying.Powder is added in the Microwave dielectric ceramic powder material 20% adhesive of quality, grinding 1 hour is granulated, crosses the sieve of 80 mesh, by powder pressing Cheng Houwei 6mm, a diameter of 13mm Thin cylinder base substrate, pressure 100MPa, sinter base substrate into porcelain at 1150 DEG C, heating rate is 3 DEG C/min, and soaking time is 3h, then furnace cooling, obtains microwave-medium ceramics.
Performance test is carried out to prepared microwave-medium ceramics, method the results are shown in Table 2 with embodiment 1.
The microwave dielectric ceramic performance of the embodiment 4~6 of table 2
Numbering x y Additive Sintering temperature εr Qf(GHz) τf(PPM/℃)
Embodiment 4 0.25 0.005 0.2% 1150℃ 36.11 59100 +0.1
Embodiment 5 0.25 0.005 0.6% 1150℃ 36.56 64500 +0.2
Embodiment 6 0.25 0.005 1% 1150℃ 36.33 59400 +0.2
Embodiment 7
X=0.1, y=0.005 is taken to weigh 92.4493g BaCO3, 7.6253g ZnO, 149.3026g TiO2With 0.6226g Nb2O5.By the raw material weighed, zirconium ball and deionized water with 1:3:2 mass ratio, with planetary mills wet method ball Mill 4 hours, after 120 DEG C of drying, in 950 DEG C of pre-burnings 3 hours (in air atmosphere), heating rate is 3 DEG C/min, cold with stove But, Preburning material is obtained.Preburning material is mixed with additive, obtains the amount of the mixture of Preburning material and additive, wherein additive For the 0.6% of Preburning material quality.
By the mixture of the Preburning material and additive, zirconium ball and deionized water with 1:3:2 mass ratio, with planet wet method Ball milling 4 hours, Microwave dielectric ceramic powder material is obtained after 120 DEG C of drying.Powder is added in the Microwave dielectric ceramic powder material 20% adhesive of quality, grinding 1 hour is granulated, crosses the sieve of 80 mesh, by powder pressing Cheng Houwei 6mm, a diameter of 13mm Thin cylinder base substrate, pressure 100MPa, sinter base substrate into porcelain at 1150 DEG C, heating rate is 3 DEG C/min, and soaking time is 3h, then furnace cooling, obtains microwave-medium ceramics.
Performance test is carried out to prepared microwave-medium ceramics, method the results are shown in Table 3 with embodiment 1.
Embodiment 8
X=0.25, y=0.005 is taken to weigh 88.4046g BaCO3, 18.2292g ZnO, 142.7705g TiO2With 0.5954g Nb2O5.By the raw material weighed, zirconium ball and deionized water with 1:3:2 mass ratio, with planetary mills wet method ball Mill 4 hours, after 120 DEG C of drying, in 950 DEG C of pre-burnings 3 hours (in air atmosphere), heating rate is 3 DEG C/min, cold with stove But, Preburning material is obtained.Preburning material is mixed with additive, obtains the amount of the mixture of Preburning material and additive, wherein additive For the 0.6% of Preburning material quality.
By the mixture of the Preburning material and additive, zirconium ball and deionized water with 1:3:2 mass ratio, with planet wet method Ball milling 4 hours, Microwave dielectric ceramic powder material is obtained after 120 DEG C of drying.Powder is added in the Microwave dielectric ceramic powder material 20% adhesive of quality, grinding 1 hour is granulated, crosses the sieve of 80 mesh, by powder pressing Cheng Houwei 6mm, a diameter of 13mm Thin cylinder base substrate, pressure 100MPa, sinter base substrate into porcelain at 1150 DEG C, heating rate is 3 DEG C/min, and soaking time is 3h, then furnace cooling, obtains microwave-medium ceramics.
Performance test is carried out to prepared microwave-medium ceramics, method the results are shown in Table 3 with embodiment 1.
Embodiment 9
X=0.4, y=0.005 is taken to weigh 84.6990g BaCO3, 27.9443g ZnO, 136.7861g TiO2With 0.5704g Nb2O5.By the raw material weighed, zirconium ball and deionized water with 1:3:2 mass ratio, with planetary mills wet method ball Mill 4 hours, after 120 DEG C of drying, in 950 DEG C of pre-burnings 3 hours (in air atmosphere), heating rate is 3 DEG C/min, cold with stove But, Preburning material is obtained.Preburning material is mixed with additive, obtains the amount of the mixture of Preburning material and additive, wherein additive For the 0.6% of Preburning material quality.
By the mixture of the Preburning material and additive, zirconium ball and deionized water with 1:3:2 mass ratio, with planet wet method Ball milling 4 hours, Microwave dielectric ceramic powder material is obtained after 120 DEG C of drying.Powder is added in the Microwave dielectric ceramic powder material 20% adhesive of quality, grinding 1 hour is granulated, crosses the sieve of 80 mesh, by powder pressing Cheng Houwei 6mm, a diameter of 13mm Thin cylinder base substrate, pressure 100MPa, sinter base substrate into porcelain at 1150 DEG C, heating rate is 3 DEG C/min, and soaking time is 3h, then furnace cooling, obtains microwave-medium ceramics.
Performance test is carried out to prepared microwave-medium ceramics, method the results are shown in Table 3 with embodiment 1.
Embodiment 10
X=0.55, y=0.005 is taken to weigh 81.2916g BaCO3, 36.8776g ZnO, 131.2832g TiO2With 0.5475g Nb2O5.By the raw material weighed, zirconium ball and deionized water with 1:3:2 mass ratio, with planetary mills wet method ball Mill 4 hours, after 120 DEG C of drying, in 950 DEG C of pre-burnings 3 hours (in air atmosphere), heating rate is 3 DEG C/min, cold with stove But, Preburning material is obtained.Preburning material is mixed with additive, obtains the amount of the mixture of Preburning material and additive, wherein additive For the 0.6% of Preburning material quality.
By the mixture of the Preburning material and additive, zirconium ball and deionized water with 1:3:2 mass ratio, with planet wet method Ball milling 4 hours, Microwave dielectric ceramic powder material is obtained after 120 DEG C of drying.Powder is added in the Microwave dielectric ceramic powder material 20% adhesive of quality, grinding 1 hour is granulated, crosses the sieve of 80 mesh, by powder pressing Cheng Houwei 6mm, a diameter of 13mm Thin cylinder base substrate, pressure 100MPa, sinter base substrate into porcelain at 1150 DEG C, heating rate is 3 DEG C/min, and soaking time is 3h, then furnace cooling, obtains microwave-medium ceramics.
Performance test is carried out to prepared microwave-medium ceramics, method the results are shown in Table 3 with embodiment 1.
Embodiment 11
X=0.7, y=0.005 is taken to weigh 78.1477g BaCO3, 45.1199g ZnO, 126.2059g TiO2With 0.5263g Nb2O5.By the raw material weighed, zirconium ball and deionized water with 1:3:2 mass ratio, with planetary mills wet method ball Mill 4 hours, after 120 DEG C of drying, in 950 DEG C of pre-burnings 3 hours (in air atmosphere), heating rate is 3 DEG C/min, cold with stove But, Preburning material is obtained.Preburning material is mixed with additive, obtains the amount of the mixture of Preburning material and additive, wherein additive For the 0.6% of Preburning material quality.
By the mixture of the Preburning material and additive, zirconium ball and deionized water with 1:3:2 mass ratio, with planet wet method Ball milling 4 hours, Microwave dielectric ceramic powder material is obtained after 120 DEG C of drying.Powder is added in the Microwave dielectric ceramic powder material 20% adhesive of quality, grinding 1 hour is granulated, crosses the sieve of 80 mesh, by powder pressing Cheng Houwei 6mm, a diameter of 13mm Thin cylinder base substrate, pressure 100MPa, sinter base substrate into porcelain at 1150 DEG C, heating rate is 3 DEG C/min, and soaking time is 3h, then furnace cooling, obtains microwave-medium ceramics.
Performance test is carried out to prepared microwave-medium ceramics, method the results are shown in Table 3 with embodiment 1.
The microwave dielectric ceramic performance of the embodiment 7~11 of table 3
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (6)

1. a kind of microwave-medium ceramics, it is characterised in that there is following chemical general formula：Ba2Zn4xTi8-2yNb2yO18+4x+y, x=0.1~ 0.7, y=0~0.01；Y is not 0；
Also include 0~1 wt% additive；The content of additive is not 0；
The preparation method of the additive is：By SiO2、B2O3, CaO, CuO and Y2O3Ball milling after mixing, it is molten in 1300~1400 DEG C Melt 10~30 min, obtain the additive.
2. microwave-medium ceramics according to claim 1, it is characterised in that：SiO used2、B2O3, CaO, CuO and Y2O3's Mass ratio is（40~55）:（25~35）:（15~30）:（2~10）:（1~10）；The technique of the ball milling is：Institute's materials： Ball：Water=1:（3~4）:（2~3）Mass ratio, the r/min of rotating speed 200~300, Ball-milling Time be 20~24 hours.
3. the preparation method of the microwave-medium ceramics described in a kind of claim 1, it is characterised in that comprise the following steps：According to Ba2Zn4xTi8-2yNb2yO18+4x+yStoichiometric proportion, wherein, x=0.1~0.7, y=0~0.01, by BaCO3、ZnO、Nb2O5With TiO2Dispensing in proportion, a ball milling and drying obtain mixed once material；Preheating, obtain Preburning material；Toward what is be prepared Additive is added in Preburning material, is dried after secondary ball milling, obtains secondary mixed material, adds binding agent, after granulating and forming, is obtained Ceramic green；Sintering, obtains microwave-medium ceramics.
4. the preparation method of microwave-medium ceramics according to claim 3, it is characterised in that：The technique of ball milling Specially：Institute's materials：Ball：Water=1:（3~4）:（2~3）Mass ratio, the r/min of rotating speed 200~300, ball milling 3~5 hours； The condition of the pre-burning is：With 3~8 DEG C/min heating rate, 800~1000 DEG C are warming up to, insulation cools down after 3~4 hours； The condition of the sintering is：1100~1300 DEG C are warming up to 3~8 DEG C/min heating rate, insulation cools down after 2~4 hours.
5. the preparation method of microwave-medium ceramics according to claim 3, it is characterised in that：The technique of the secondary ball milling Specially：Institute's materials：Ball：Water=1:（3~4）:（2~3）Mass ratio, the r/min of rotating speed 200~300, ball milling 3~5 hours.
6. the preparation method of microwave-medium ceramics according to claim 3, it is characterised in that：Described binding agent is quality Percentage composition is 6~8% polyvinyl alcohol water solution；The addition of the binding agent is 15~25 % of reaction system gross mass； Described drying is to be dried at 80~150 DEG C.
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